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Eingeladener Vortrag
- nein (84)
Heavy gases in large quantities are used worldwide in various industries. Past incidents, such as
the liquefied gas disaster in Viareggio (2009) have shown that these materials are difficult to
handle in a safe manner. According to the German Hazardous Incident Ordinance (StörfallVO
2000 - 12. BImSchV) plant operators with 'extended responsibilities' must produce a report in
which they verify that, in the event of an unintentional gas release, the surrounding area will not
be aversely affected. The essential elements of this report include calculations of both released
mass flow and gas dispersion. Using models such as the VDI guideline 3783 (state of the art in
Germany) plant operators are able to predict the characteristics of likely gas dispersions.
Within the framework of the reported experimental trials, the release process of heavy gases
from standard gas cylinders was investigated. Using the results of this investigation a calculation
methodology has been developed which is able to predict the mass flow of a gas-phase release.
As input parameters only the geometry of the gas cylinder, the material properties of the
respective fluid as well as the environmental parameters such as velocity of approach and air
temperature are required. In the course of modeling various approaches for nucleate boiling have
been tested for their applicability. Both the calculation methodology and a comparison between
the calculated and experimental results will be presented.
Within the same framework of experimental trials, the dispersion process of the aforementioned
heavy gases was also investigated. The dispersed gas cloud in this case was considered as originating from a continuous point source under ambient conditions. For the various trials
concentrations both in the heavy gas (≥ 1 vol.-%) and in the neutral gas field (≤ 3000 ppm) were
measured. In the immediate area of the release the length, width and height of the heavy gas
cloud were evaluated. The experimental results, comparison calculations and the measurement
techniques will be presented.
Heavy gases in large quantities are used worldwide in various industries. Past incidents, such as the liquefied gas disaster in Viareggio (2009) have shown that these materials are difficult to handle in a safe manner. According to the German Hazardous Incident Ordinance (StörfallVO 2000 - 12. BIMSchV), plant operators with extended responsibilities must produce a report in which they verify that , in the event of an unintentional gas release, the surrounding area will not be aversely affected. Essential elements of this report are calculations of both the released mass flow and the gas dispersion. Using models such as the VDI guideline 3783 (state of the art in Germany) plant operators are able to predict the characteristics of likely gas dispersions. The presented experimental investigations were carried out at the BAM better understand heavy gas dispersion with high gas concentrations in the air (≥ 1 Vol.-%), as well as concentrations with approximately neutral density characteristics (≤ 3000ppm) in order to test the accuracy of the VDI guideline. The starting point for experimental trials was the heavy gas releases resulting from pipeline, vessel or standard gas bottle leaks, with mass flows of between 20 and 100 g s-1. Investigations on the gas-phase release process focused on the unsteady mass flow associated with releases from standard gas bottles. The experimental results will be used as comparative parameters for future simulations. The goal of these simulations is to develop a model with which calculation of the unsteady mass flow, based on the material characteristics for any gas, is possible.
Für den sicheren Betrieb von Brennstoffzellen und für die Hochdruckwasserelektrolyse wurden die Explosionsgrenzen und Explosionsdrücke von Wasserstoff und Wasserstoff/Methan-Gemischen bei Anfangsdrücken von bis zu 200 bar gemessen. Der Bericht gibt eine Übersicht über die Druck- und Temperaturabhängigkeiten der Explosionsbereiche mit Luft und Sauerstoff als oxidierende Komponenten. Dabei waren ebenfalls die Grenzwerte zur Inertisierung der Gemische mit Stickstoff von Interesse. Für den sicheren Umgang mit Wasserstoff bei atmosphärischen Bedingungen sind die Dreistoffsysteme Brenngas/Stickstoff/Luft zusätzlich nach einer neuen europäischen Norm (prEN 1839) bestimmt worden.
Explosionsgrenzen von Wasserstoff/Sauerstoff-Gemischen (Abschlussbericht zum Vorhaben VH2226)
(2002)
Messung und Simulation des Inertgaseinflusses auf Explosionsgrenzen bei erhöhten Anfangsdrücken
(2001)
Messung und Simulation des Inertgaseinflusses auf Explosionsgrenzen bei erhöhten Anfangsdrücken
(2001)
Eine neue Bestimmungsmethode für Sauerstoffäquivalenzkoeffizienten von oxidierend wirkenden Gasen
(1998)
In der vorliegenden Arbeit wird die sicherheitstechnische Eigenschaft "Entzündlichkeit" von
Gasen und Gasgemischen vorgestellt. Die Definitionen und Prüfverfahren in den
unterschiedlichen technischen Rechtsbereichen werden erläutert. Zur Klassifizierung von
Gasgemischen in kleineren Mengen ist sowohl im europäischen Gefahrstoff-, als auch im
Gefahrgutrecht ein Rechenverfahren nach ISO 10156, Nr. 4.6, zulässig. Für die Anwendung
des Rechenverfahrens benötigt man Stoffkenngrößen (Tci, Kk), die im Anhang zur ISO 10156
für einige Stoffe aufgelistet sind. Im Rahmen einer Forschungskooperation wurden im
europäischen Kernforschungszentrum (CERN) in Genf, an der Uni-GH Paderborn und in der
BAM Explosionsbereiche von Dreistoffsystemen (Brenngas, Inertgas, Luft) nach DIN 51649
bestimmt, aus denen sich Tci- sowie KK-Werte berechnen lassen. Die so mit einheitlichen
Apparaturen und Prüfverfahren ermittelten Werte weichen z.T. erheblich von den Angaben
der ISO 10156 ab. Im letzten Abschnitt dieser Arbeit werden Druck- und Temperatureinfluss
auf die Entzündlichkeit diskutiert.
Eine rechnergesteuerte Apparatur zur Bestimmung der Explosionsgrenzen von Gasen und Gasgemischen
(1995)
Klassifizierung von Gasgemischen - ein Verfahren zur experimentellen Bestimmung von Tci-Werten
(1997)
Ermittlung von Kenngrößen für die Druckentlastung von Gasexplosionen bei höheren Anfangsdrücken
(2001)
At Juelich Research Center the prototype of an alkaline 120-bar electrolyser has been developed and built. Constructive and process-engineering measures must be taken to ensure the safe operation of such facilities. Potential hazards occur due to the high operating pressure in conjunction with the reactivity of the product gases and the electrolyte. First of all, the operating mode and technical features of the Juelich high-pressure electrolyser will be dealt with. Within the framework of a parametric study, the potential for weight reduction of the prototype while observing the rules for pressure vessel design will be shown. The Federal Institute for Materials Research and Testing in Berlin has performed measurements concerning the explosion limits of H2/O2 mixtures at different temperatures and pressures up to 200 bars. At an electrolysis test rig of IWV-3, which can also be operated up to 200 bars, investigations were carried out concerning the gas composition on the H2 and O2 path under different operating conditions. These measurement series were compared to the explosion limits determined and evaluated to derive safety measures required for the operation of high-pressure electrolysers.
Evaluation of Standard Test Methods for the Determination of Explosion Limits of Gases and Vapors
(2004)
Zündgrenzen von Wasserstoff-Sauerstoff-Wasserdampfgemischen unter SWR-typischen Randbedingungen
(2004)
The project will develop test methodology for explosion indices al non-ambient conditions, a validated data base on them and on many other explosion indices as a function of pressure and temperature. Further, models will be developed, enabling prediction of behaviour of reactive systems and predicting explosion parameters.
An important method to prevent fires and explosions is to avoid explosive fuel-air mixtures. For this purpose the exact knowledge of the explosion range is required as a function of the combustible, oxidizer and inert gas concentrations. Frequently triangular diagrams are used in order to display the explosion range of such three component gas mixtures. Beside the explosion limits and the explosion range other characteristics can be deduced from explosion diagrams. More than 200 of such explosion diagrams are available in the database CHEMSAFE®, included among others. The in-house version of the database is able to provide all characteristics of a chosen system by means of a TRIANGLE-software. Furthermore a recently published German data book contains 158 explosion diagrams. Many diagrams were measured according to the German DIN 51649 standard. Other systems are available for elevated initial pressures and temperatures. This paper describes how to use the TRIANGLE software for flammability diagrams and the meaning and use of derived characteristics (MOC, MXC, MAI) for explosion prevention. Furthermore a calculation method for the flammability of gas mixtures is shown using the MXC values.
Evaluation of Standard Test Methods for the Determination of Explosion Limits of Gases and Vapours
(2004)
Biogas is an important source of renewable energy. It consists mainly of methane and carbon dioxide, with low levels of hydrogen sulphide and other gases. That means, that the toxicological aspects and the flammability of biogas has to be taken into account. A serious accident has happened just recently in a biogas production plant in Germany, accompanied with injuries and four totalities. The methane content of the different types of biogases varies from about 82 % till 40 % and the rest is mostly carbon dioxide with trace gases depending on the anaerobe digestion process. These plants must also be controlled to avoid pollution and the risk of explosion. The 1999/92/EC Directive (ATEX 137) addressed to employer. The employer of such plants needs to implement safety requirements, such as prevention of explosive atmospheres, avoiding ignition sources, etc. In addition he has to prepare an explosion protection document and carry out a hazard assessment. The basic information for these documents based on the safety characteristics of the produced gases. These data can be taken e. g. from the database CHEMSAFE® using explosion diagrams of methane/carbon dioxide/air mixtures. In the literature the biogas explosion limits often presented in a confusing way. In this presentation a simple method will be shown to get correct values by correlation of the explosion limits with the methane content of the biogas. While biogas production will be forecast with an acceleration of growth in the future, it is essential to clear this important safety problem.
Explosionsgrenzen der Zerfallsreaktion von Gemischen aus Ethylenoxid, Propylenoxid und Stickstoff
(2007)
International and European dangerous substances and dangerous goods regulations refer to the standard ISO 10156 (1996). This standard includes a test method and a calculation procedure for the determination of the flammability of gases and gas mixtures in air. The substance indices for the calculation, the so called Tci values, which characterise the fire potential, are provided as well. These ISO Tci values are derived from explosion diagrams of older literature sources which do not take into account the test method and the test apparatus. However, since the explosion limits are influenced by apparatus parameters, the Tci values and lower explosion limits, given by the ISO tables, are inconsistent with those measured according to the test method of the same standard. In consequence, applying the ISO Tci values can result in wrong classifications. In this paper internationally accepted explosion limit test methods were evaluated and Tci values were derived from explosion diagrams. Therefore, an open vessel method with flame propagation criterion was favoured. These values were compared with the Tci values listed in ISO 10156. In most cases, significant deviations were found. A detailed study about the influence of inert gases on flammability is the objective of Part 2.
Ternary systems, which contain flammable gas, inert gas and air, were studied in order to give the user an evaluation of the ISO 10156 calculation method for the flammability of gas mixtures. While in Part 1 of this article the fire potential of flammable gases was the focal point, the influence of inert gases on the flammability of gas mixtures was studied in Part 2. The inerting capacity of an inert gas is expressed by the dimensionless K value, the so-called coefficient of nitrogen equivalency. The experimental determination of K values is demonstrated by using explosion diagrams. The objective of this study was to compare the estimated results, given by ISO 10156, with measurements of explosion ranges based on the German standard DIN 51649-1, given by CERN and CHEMSAFE. The comparison shows that ISO 10156, Table 1, supplies conservative K values, which can be regarded as safe in all cases. Nevertheless, in a number of cases ISO underestimates the inerting capacity, so that non-flammable gas mixtures are considered flammable.
The knowledge of the explosion limits of biogases in air is necessary to define explosion protection measures. Biogases from agricultural plants vary however in their composition, so that for each gas composition the explosion limits would have to be measured. Frequently the explosion limits of biogas are therefore referred in the safety-relevant literature only to the methane fraction of the gas mixture, without indicating this additionally. This leads to the fact that the explosion ranges for the total mixture consists of methane, carbon dioxide and further residual gases are falsely specified.
For this reason a simple method is presented in the following, which show, how the explosion limits of a biogas can be determined from its methane content using an explosion diagram of methane/carbon dioxide/air system. The explosion diagram was measured according to the German Standard DIN 51649-1.
The presented calculation method supplies however correct results only if the nitrogen fraction in the biogas does not exceed approx. 5 % by volume.
Chemically unstable gases - flammability of ethylene oxide mixtures in sterilization processes
(2008)
In der Prozesstechnik kommt es immer wieder zu Zündungen durch Druckstöße mit Gasen. Bekannt ist dieses Phänomen vom Umgang mit Sauerstoff im Kontakt mit nicht geeigneten Materialien. Aber auch andere Gase, z. B. Acetylen, können durch schnelle Kompression gezündet werden. In der vorliegenden Arbeit werden, in Fortführung früherer Untersuchungen in Rohren, solche Zündvorgänge mit Hilfe von Zündtemperaturen abgeschätzt.
Die Kenntnisse der Einflüsse von Druck, Temperatur und Oxidationsmittel auf sicherheitstechnische Kenngrößen wie Explosionsgrenzen sind eine notwendige Voraussetzung, um zu entscheiden, ob mit den bei atmosphärischen Bedingungen geltenden Kenngrößen eine ausreichende Sicherheit zu gewährleisten ist. Dies wird anhand von Beispielen erklärt und die Konsequenzen für die praktische Anwendung in der Industrie diskutiert.
Chemically unstable gases - flammability of ethylene oxide mixtures in sterilization processes
(2008)
For the assessment of explosion hazards by industrial
sterilization processes with ethylene oxide (EO), the flammability
regions of 3-component systems EO/nitrogen/air, EO/carbon
dioxide/air and EO/water vapor/air were determined. The tests were
performed at temperatures of 20 °C and 100 °C and at pressures of
40 kPa and 100 kPa in accordance with the standard test method EN
1839-B.
The observed flammability regions are similar in shape and
typical for mixtures with ethylene oxide. According to the molecular
heat capacities the regions get larger with nitrogen and smaller with
carbon dioxide. They become larger with increasing pressure and
increasing temperature.
Using experimental data a semi-empirical model was created
that allows the calculation of flammability limits of process gases in
sterilization processes. Such process gases can consist of EO,
nitrogen, carbon dioxide, water vapor and air.
The model is based on the assumption that the adiabatic flame
temperatures along the boundary curves of a flammability region
have a certain temperature profile that is nearly independent of the
type of the inert gas. The adiabatic flame temperatures were
calculated by using the Gaseq Code.
Using a temperature profile calculated from only one
experimental system EO/inert gas/air it is possible to predict the
flammability limits of systems with other inert gases or of process
gases containing several inert gases.
Für die sicherheitstechnische Beurteilung von Sterilisationsprozessen wurden die Explosionsgrenzen von Gasgemischen aus Ethylenoxid, Inertgas und Luft experimentell bestimmt. Die Messungen sind mit Stickstoff, Kohlenstoffdioxid und Wasserdampf bei 20 und 100 °C sowie bei 0,4 und 1,0 bar durchgeführt worden. Mit Hilfe der Daten wurde ein halbempirisches Modell entwickelt, mit dem die Explosionsfähigkeit von Prozessgasgemischen berechnet werden kann.
Es wurde ein Verfahren zur Berechnung von Explosionsgrenzen ethylenoxidhaltiger Gasphasen in Sterilisatoren entwickelt. Mit Hilfe der Software GasEq® und des neu entwickelten Makros SterEx für MS-Excel® lassen sich die Explosionsgrenzen für Gemische aus Ethylenoxid, Luft und Inertgasen bei Temperaturen zwischen 20°C und 100°C sowie 0,4 bar und 1,0 bar berechnen. Somit ist es schnell möglich, sichere Betriebsbedingungen für Sterilisationsprozesse mit Ethylenoxid festzulegen. Das halbempirische Modell basiert auf der Annahme konstanter Flammentemperaturprofile an den Explosionsgrenzen in Abhängigkeit der EO-Konzentration für verschiedene Gemische. Durch systematische Zündversuche wurden Explosionsgrenzen für Gemische aus Ethylenoxid, Stickstoff, Kohlenstoffdioxid, Wasserdampf und Luft zur Bestimmung von Modellparametern und zur Validierung des Verfahrens bestimmt. Um die Prozessbedingungen in Sterilisatoren möglichst genau zu simulieren, wurden die Versuche in einem geschlossenen Autoklav in Anlehnung an DIN EN 1839-B durchgeführt. Berechnungen der Explosionsgrenzen von Prozessgasgemischen mit SterEx ergeben eine gute Übereinstimmung mit experimentell ermittelten Werten.
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A calculation method for flammability limits of gas phases with ethylene oxide in sterilisers was developed. Using the Software GasEq® and the newly developed Makro SterEx for MS-Excel®, flammability limits of mixtures with ethylene oxide, air and inert gases at temperatures between 20°C and 100°C and pressures between 0.4 bar and 1.0 bar can be calculated. This method can be used to easily determine safe operating conditions. The used semi-empirical model is based upon the assumption of constant flame temperature profiles at the flammability limits subject to the EO-concentration for different mixtures. To collect model parameters and to validate the model, several experiments with mixtures of ethylene oxide, nitrogen, carbon dioxide, water vapour and air were carried out to determine flammability limits. To simulate the structural conditions of sterilisers, the experiments were conducted in accordance to DIN EN 1839-B in a closed autoclave with temperatures and pressures relevant for sterilisation processes. The calculation of flammability limits of process gas mixtures with SterEx provides good agreement with flammability limits that were determined in experiments.
In der europäischen Richtlinie 2009/31/EG über die geologische Speicherung von Kohlendioxid wird das CCS-Verfahren (carbon dioxide capture and geological storage) als eine Brückentechnologie bezeichnet, die zur Abschwächung des Klimawandels beiträgt. Sowohl bei den Techniken zur Abscheidung des CO2 im Kraftwerk, als auch beim Transport und bei der geologischen Speicherung sind sicherheitstechnische Fragen zu beachten, um das Risiko einer Freisetzung großer Mengen an CO2 zu minimieren. Dabei ist, neben den neu entwickelten Technologien, der Umgang mit sehr großen Mengen von Verbrennungsabgasen und Kohlendioxid zu bewerten.
Bestimmung der Explosionsgrenzen von Gasen und Dämpfen - Ein Vergleich von 4 Standardverfahren
(2002)
Bestimmung der Explosionsgrenzen von Gasen und Dämpfen - Ein Vergleich von 4 Standardverfahren
(2002)
An important method to prevent fires and explosions is to avoid explosive fuel-air mixtures. For this purpose the exact knowledge of the explosion range is required as a function of the combustible, oxidizer and inert gas concentrations. Frequently triangular diagrams are used in order to display the explosion range. This paper describes how to use the TRIANGLE software for flammability diagrams. Furthermore a calculation method for the flammability of gas mixtures is shown.
Für den Explosionsschutz in Biogasanlagen ist es erforderlich, die Explosionsgrenzen des Gases in Luft zu kennen. Biogase aus landwirtschaftlichen Anlagen haben jedoch eine schwankende Zusammensetzung, sodass für jede Gemischzusammensetzung die Explosionsgrenzen experimentell bestimmt werden müssten. Dies ist i. d. R. mit erheblichem Aufwand verbunden. In diesem Beitrag wird eine Methode vorgestellt, bei der mithilfe von zwei Explosionsdiagrammen die Explosionsgrenzen von Biogas mit bekannter Zusammensetzung abgeschätzt werden können. Dabei werden neben dem Methan- und Kohlendioxidanteil des Biogases auch mögliche Anteile von Wasserdampf berücksichtigt.
The data book "Safety Characteristic Data" is published in two volumes. In the first volume "Flammable Liquids and Gases" the safety characteristics of pure substances in mixture with air have been published. In Volume 2 "Explosion Regions of Gas Mixtures" the properties of gaseous fuel/inert gas/oxidiser mixtures are in the centre of interests. For the first time complete data sets of the explosion regions of gaseous mixtures are available in a printed format as needed by authorities and industry. Dangerous explosive compositions can be detected by such explosion diagrams. Therefore they are the basis of primary explosion protection, e.g. to prevent explosive mixtures by inertisation.-------------------------------------------------------------------------------------
Das Tabellenwerk "Sicherheitstechnische Kenngrößen" ist in zwei Bänden herausgegeben worden. Während im ersten Band "Brennbare Flüssigkeiten und Gase" vorrangig die sicherheitstechnischen Kenngrößen reiner Stoffe im Gemisch mit Luft behandelt werden, stehen im Band 2 "Explosionsbereiche von Gasgemischen" die Eigenschaften von Gemischen aus Brenngas, Oxidator und Inertgas im Mittelpunkt. Damit soll erstmals dem Wunsch von Industrie und Behörden entsprochen werden, in einem Tabellenwerk komplette Datensätze zu den Explosionsbereichen von Stoffgemischen in gedruckter Form zur Verfügung zu stellen. Den Explosionsdiagrammen kann man die Zusammensetzung von explosionsfähigen Gemischen entnehmen. Sie sind damit Grundlage für Maßnahmen des primären Explosionsschutzes, z. B. für die Inertisierung.