2.2 Prozesssimulation
Filtern
Dokumenttyp
- Vortrag (30)
Sprache
- Englisch (18)
- Deutsch (11)
- Mehrsprachig (1)
Referierte Publikation
- nein (30)
Schlagworte
- CLP (7)
- GHS (6)
- Einstufung (5)
- Dangerous Goods (4)
- Kennzeichnung (4)
- Prüfmethoden (4)
- Alternative Antriebe (3)
- Behälterversagen (3)
- Fahrzeugbrand (3)
- Gefahrenklasse (3)
Organisationseinheit der BAM
- 2 Prozess- und Anlagensicherheit (30)
- 2.2 Prozesssimulation (30)
- 2.1 Sicherheit von Energieträgern (3)
- 3 Gefahrgutumschließungen; Energiespeicher (3)
- 8 Zerstörungsfreie Prüfung (3)
- 8.1 Sensorik, mess- und prüftechnische Verfahren (3)
- 2.0 Abteilungsleitung und andere (2)
- 3.0 Abteilungsleitung und andere (2)
- 3.2 Gefahrguttanks und Unfallmechanik (1)
Eingeladener Vortrag
- nein (30) (entfernen)
One of the fundamental principles of the UN-GHS (Globally Harmonized System of Classification and Labelling of Chemicals) is that all hazards of a chemical should be assigned and communicated. There is no general prioritization of hazards in the sense that certain hazard classes are not applicable if another one has been assigned. In contrast to health and environmental hazards, there are physical or chemical factors which preclude certain combinations of physical hazard classes. So far, there is no common understanding as to which combinations are relevant and which not. For example, should a pyrophoric liquid be classified as flammable liquid in addition, or is this redundant and unnecessary? In the course of the implementation of the GHS by countries or sectors and the actual application by industry all over the world, such questions become more and more important. For many of the combinations an unambiguous decision based on theGHS alone is not possible, thus confirming that the question which physical hazard classes might be assigned simultaneously to a chemical is not trivial. As one more milestone on the path to a globally harmonized system for the classification of hazardous chemicals, this should be discussed and ultimately solved on a global basis. It is the hope that this presentaion might serve as an impetus for such discussions.
Transposition of regulations of the (German) employer’s liability insurance association (BGV’n) into Federal responsibility.
Fundamentals are regulated in the German Hazardous Substances Ordinance (GefStoffV). Prospectively, some definitions and more details are specified in a Technical Rule (TRGS 741 „Organic Peroxides“). A second project outline was discussed in 2014; because of some formal objections concerning the process and, particularly, the membership in a project group, no progress et al. since 2014.
Nevertheless, the BGV B4 is still valid. Because of some new findings and new test results a revision and Supplementation of the table of assignments of OP to risk (storage) groups was required.
Summary of recent research activities at BAM concerning large scale fireballs of organic peroxides (OP). Videos of the tests performed in Nanjing, China, are presented. A new model for OP fireball diameter, duration, height and SEP is proposed based on all experiments. In addition, small scale test results using DTBP and heptane are presented. Finally, CFD simulation is used to predict the fireball parameters: diameter, duration and height.
Biozidprodukte unterliegen einer Zulassungspflicht, bevor sie verkauft oder angewendet werden dürfen. Zulassungsanträgen für Biozidproduktfamilien sowie für in-situ-Systeme müssen als IUCLID-Dossiers eingereicht werden. Hierfür müssen bestimmte Informationsanforderungen zur Bewertung der Gefahren vorgelegt werden. Wenn jedoch keine experimentellen Daten ermittelt wurden, muss eine valide Begründung für den Datenverzicht vorgelegt werden. Für die physikalischen Gefahren wird das „waiving of testing“ vorgestellt, insbesondere wird die Vorgehensweise in IUCLID erläutert.
Chemikalien werden im Prüflabor auf ihre gefährlichen Eigenschaften getestet, um die Risiken bei deren Handhabung richtig abschätzen zu können. Dazu sind Prüfmethoden entwickelt und veröffentlicht worden, die heute weltweit Anwendung finden. Auf die Validität der jeweiligen Prüfmethode und richtige Durchführung der Prüfung und Bewertung im Laboratorium müssen sich Hersteller, Importeure, Händler, Arbeitgeber oder Verbraucher verlassen können.
Die Bundesanstalt für Materialforschung und –prüfung (BAM), Berlin hat eine langjährige Erfahrung sowohl bei der Ermittlung und Bewertung der physikalischen Gefahren von Chemikalien als auch bei der Einstufung und Kennzeichnung nach dem Chemikalienrecht (z.B. gemäß REACH-VO, CLP-VO, Gefahrgutvorschriften u.a.).
Es werden drei Poster präsentiert, welche einerseits kritisch die im Rahmen der chemikalienrechtlichen Verfahren von den Registranten vorgelegten Prüfergebnisse / Prüfberichte bewerten und andererseits die Zuverlässigkeit von verschiedenen Prüfmethoden einschätzen bzw. den Aufwand am Beispiel der Validierung einer konkreten Prüfmethode durch Ringversuche demonstrieren.
REACH-Registrierungsdossiers z.B. werden mit der Softwareanwendung IUCLID (International Uniform Chemical Information Database) erstellt. Für die Behörden ist die Bewertung der Zuverlässigkeit mit den Informationen zu den Studien im IUCLID-Dossiers oftmals schwer nachvollziehbar.
Bei der Bewertung der Verlässlichkeit der im Labor gewonnenen Prüfergebnisse spielen Ringversuche eine entscheidende Rolle. In den letzten 10 Jahren wurden von der BAM und der PTB Ringversuche zu verschiedenen Prüfmethoden durchgeführt. In allen Ringversuchen wurden deutliche Unterschiede zwischen den Ergebnissen der teilnehmenden Laboratorien festgestellt. Die Abweichungen der Prüfergebnisse wurden jedoch nicht nur durch Laborfehler, sondern auch durch Mängel der Prüfmethoden verursacht. Deshalb ist es wichtig zu wissen, wie gut die Prüfmethode ist, mit der ein Gefahrgut oder Gefahrstoff klassifiziert wird oder mit denen sicherheitstechnische Kenndaten bestimmt werden.
Ringversuche werden bei der Methodenentwicklung und -validierung eingesetzt und können zur Ermittlung der Messunsicherheit genutzt werden. Validierungsberichte zu Prüfmethoden sorgen für Transparenz, sind für die Regulierung im Chemikalienrecht erforderlich und dienen auch dazu auf globaler Ebene gleiche Wettbewerbsbedingungen zu schaffen.
Die BAM und die PTB unterstützen deshalb den weiteren Ausbau des Ringversuchsprogramms des im Jahr 2007 gegründeten Kompetenzzentrums zur Qualitätssicherung für Prüfungen von Gefahrgütern und Gefahrstoffen auf physikalische Gefahren (Centre for quality assurance for testing of dangerous goods and hazardous substances, CEQAT-DGHS, www.ceqat-dghs.bam.de). Dieses betreibt die BAM gemeinsam mit der PTB und der QuoData Gesellschaft für Qualitätsmanagement und Statistik mbH, Dresden.
Self-Accelerating Decomposition Temperature (SADT) is a safety characteristic for the transport of self-reactive substances and organic peroxides. Its determination is time-consuming and in dependence on the test method also material-consuming. As shown previously, DSC measurements, which can be carried out fast and with a few milligram of material, supply a good correlation with SADT for technical pure, liquid organic peroxides. The approach is now applied for solid organic peroxides. Besides, the parameters, which are involved in the correlation, are discussed and their effect on the result is weighted qualitatively. In addition it was shown, that the method is inapplicable in an easy manner for diluted organic peroxides and pure self-reactive substances.
In continuation of a preceding test series involving sole LPG vehicle tanks, three passenger cars equipped with identical toroidal steel LPG tanks were set on fire. The tanks were installed in the space normally reserved for the spare tyre, in the car boot. No safety device was installed on the tank, in order to force critical failure of the cylinder. Two of the cars were equipped with a tank filled with liquefied propane to a level of 20% (5.3 kg), the third one was filled completely (25.5 kg). The partially filled tanks failed critically within a time period of more than 20 min after the initiation of the fire. The fully-filled tank did not rupture; the propane was released continuously through a small leak that appeared during the fire. Comprehensive equipment was used to procure measurement data, enabling an analysis of potential consequences and hazards to humans and infrastructure within the vehicle surroundings. The inner status of the tank (pressure, temperature of the liquid phase and the steel casing), the development of the fire (temperature inside and around the vehicle) and the pressure induced in the near-field in case of tank rupture were recorded. The results were analysed in detail and compared against the data gained in tests involving sole, but identical LPG tanks.
Der Vortrag vermittelt einen Überblick über die physikalischen Gefahren nach der CLP-Verordnung (Verordnung (EG) Nr. 1272/2008), die Schnittstelle zum global harmonisierten System zur Einstufung und Kennzeichnung auf Grundlage des UN Manual of Tests and Criteria, die Bedeutung der Qualitätssicherung bei Prüfungen auf physikalische Gefahren, sowie die Prüf- und Bewertungsstrategien und welche Tests dabei unverzichtbar sind.
Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances
(2019)
Due to the fast development and availability of computers, predictive approaches are increasingly used in the evaluation process of hazardous substances complementary to experiments. Their use was recommended as alternative to experimental testing by the REACH regulation to complete the lack of knowledge on properties for existing substances that must be registered before 2018 (upon quantities). Among the proposed predictive approaches, Quantitative Structure Property Relationships (QSPR) are powerful methods to predict macroscopic properties from the only molecular structure of substances.
In that context, the HAZPRED project (2015-2018, founded by the SAF€RA consortium) aims to develop theoretical models (e.g. QSPR) and small-scale tests to predict complex physico-chemical properties (e.g. thermal stability, explosivity) of hazardous substances to complete the lack of knowledge on these hazardous substances quickly or to understand their decomposition behaviour better.
In particular, this contribution will present the work done in this project on the physical hazards of organic peroxides and self-reactive substances: gathering of existing experimental data, new experimental campaigns, review of existing models and proposition of new estimation methods.
Final report of research activities at BAM concerning large scale fireballs of organic peroxides (OP). New models for OP fireball diameter, duration, height and Surface Emmissive Power (SEP) are proposed and discussed based on a large number of large-scale and small-scale experiments using Di-tert-butylperoxide (DTBP) as a liquid OP and heptane as a liquid hydrocarbon fuel. Finally, CFD simulations are used to predict the fireball parameters: diameter, duration, height and SEP. Also the impact on the German storage regulations for organic peroxides are discussed.
Der Fokus des Beitrages bestand darin, die BAM, insbesondere die Abteilung 2 (Chemische Sicherheitstechnik) als möglichen Projektpartner im Rahmen von Horizont 2020 "Sichere Gesellschaften" zu präsentieren. Dabei wurden die Kernkompetenzen der Abteilung 2, die Kooperationen zu anderen Abteilungen in der BAM bzw. einige Beispiele zu bisherigen Projekterfahrungen, hinsichtlich dem Aktivitätsfeld "Security" vorgestellt.
Prüfapparaturen zur Bestimmung sicherheitstechnischer Kennzahlen müssen präzise messen, um verlässliche Ergebnisse zu produzieren. Oftmals gibt es in der Methodenbeschreibung allerdings keine Informationen zu Messunsicherheiten o.ä.. In dem Vortrag werden Ringversuchsprogramme das CEQAT-DGHS beschrieben und aktuelle Arbeiten zu Verifizierungsverfahren von Messmethoden beschrieben.
In den letzten Jahren kam es auf einigen Seeschiffen zu exothermen Zersetzung von Düngemitteln und damit zu Gefährdungen von Personen und der Umwelt. Dieses führte international bei der IMO (International Maritim Organisation) zu Diskussionen hinsichtlich der Einstufungskriterien von Ammoniumnitrat und ammoniumnitrathaltigen Gemischen, den Prüfungen und den Anforderungen an den sicheren Transport; vor allem mit Seeschiffen.
Introduction: Mass transport at gas/liquid interfaces depends on many factors including the gas and liquid properties and hydrodynamics. The mass transport of a gas through the liquid is a limiting step in many chemical reactions. To gain a fundamental understanding of multiphase interfaces, the rate of mass transfer has been measured for pure gases (H2, N2, O2, He) into a thin liquid film with a well-defined surface area and velocity profile. This enables the mass transfer rate to be broken down into one parameter, which is the gas/liquid interfacial area (a), and a second parameter, which is the mass transfer coefficient (kL). Using gases with varying diffusion coefficients enables a comparison of the measured rates of mass transport to the rates predicted by film theory and penetration theory.
Method: A gravity-driven thin water film 0.000180 m in thickness flowing along the outer surface of a capillary was contacted with a gas phase inside a closed system. The liquid was circulated continuously until it was saturated with gas and the equilibrium pressure was reached. In this device, there is laminar flow, and therefore, the hydrodynamics of the liquid film are well defined.
Results: Penetration theory predicts a non-linear relationship between diffusion coefficient (DAB) and mass transfer coefficient (kL). by means of falling film reactor the actual rates of gas-liquid mass transfer are higher than those predicted by theory. Also, a linear relationship between DAB and kL is observed experimentally. The mass transfer coefficient can even, as a rule of thumb, be assumed to be relatively constant with a value of around 10-4 m/s for aqueous solutions.
Introduction: Homogenously catalyzed reactions in multiphase systems, as they are used for example for the hydroformylation or reductive amination, offer a promising approach to produce base chemicals from renewable resources. The organic and gaseous educts react with the catalyst, which is designed to be soluble in water to provide a good separation from the likewise organic products. In the resulting gas/liquid/liquid systems, the reaction is controlled through interfacial and transport phenomena. These processes fail for long chained olefins – e.g. vegetable oils and fats – because of their low solubility in water. Therefore, surfactants can be added as an emulsifier to form micellar emulsion systems (MES) [1], increase reaction speed [2] and facilitate phase separation [3]. These systems form up to three liquid phases, depending on temperature and composition. For fast reactions, the gas/liquid mass transfer plays an important role. Due to the multiple phases present, the dispersion conditions of the particles and the resulting mass transfer are complex.
Methods: In this work, the mass transfer in MES is investigated. For simplicity, only the non-reactive material system without catalyst consisting of water, dodecane and the non-ionic surfactant Marlophen NP8 was investigated. Hydrogen was applied as gas phase. The phase behavior of the MES was characterized using settling experiments and by measuring the conductivity of the emulsions [4]. The mass transfer experiments were conducted in two different setups employing the dynamic pressure method.
In a pressurized stirred tank reactor, the mass transfer performance of the whole MES was determined under the complex dispersion conditions and a variety of different system parameters by measuring the volumetric mass transfer coefficient (kLa). The specific transfer area (a) was determined measuring gas hold-up and using optical endoscope measurements [5] to record bubble sizes. The non-spherical bubbles were analyzed with a trained convolutional neural network [6].
Using a falling film capillary in a closed pressurized system [7], the mass transfer of the single phases appearing in MES were quantified. The phases were removed and investigated separately after the settling experiments. A gravity-driven laminar flow with well-defined transfer area was established along the capillary and by measuring the pressure drop over time the mass transfer coefficient (kL) could be calculated.
Results: The mass transfer coefficients of hydrogen in the single phases of the micellar emulsion system covered a broad range. The kL of the aqueous phase was similar to pure water, while the third, bi-continuous phase forming in MES had very small kL values due to its high viscosity. The mass transfer coefficient of the organic phase was found to be far higher than of the aqueous phase.
In the stirred tank reactor, different phases formed the continuous phase in the whole MES mixture for the temperature range investigated. The fastest mass transfer was found for a continuous aqueous phase below 87 °C. At higher temperatures, a phase inversion occurred, and the organic phase became continuous. The high kL of the organic phase measured in the falling film contactor did not translate directly to a higher kLa in the stirred tank reactor as the value dropped compared to an aqueous continuous phase present. The change in continuous phase were found to affect the drop and bubble sizes in the system. For an organic continuous phase, the Sauter mean diameter of the bubbles were larger and the transfer area smaller, which was the main reason for the reduced kLa.
Organic peroxide and self-reactive are classified into seven types according to their hazards. In order to determine the substance type, it is necessary to determine the properties based on test methods. The types range from type A, which is not accepted for transport in the packing in which it is tested, to type G, which is exempted from the provisions for organic peroxides or self-reactive substances.
The presentation will give an overview of the testing required for physical hazards under the BPR and CLP Regulations (Regulation (EU) No 528/2012 and Regulation (EC) No 1272/2008), safety characteristics, actual Standards and the UN Manual of Tests and Criteria as well, the importance of quality assurance in testing and data reporting, and the testing and assessment strategies on topics that have been specifically asked by EU Member States.
Differential Scanning Calorimetry (DSC) may be used to avoid testing for explosive and self-reactive properties according to the legal regulations of chemicals substances and dangerous goods.
Demonstrated measured exothermic decomposition energy value significantly affected by numerous factors - choice of sample vessel, sample mass, baseline shape, peak shape, heating rate.