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Organisationseinheit der BAM
Eingeladener Vortrag
- nein (22)
Tests according to the UN Recommendations on the Transport of Dangerous Goods for the determination of explosive properties of organic peroxides have been compared with screening criteria for explosivity based on measurements in a closed mini-autoclave (MCPVT). It will be shown that an additional screening test may be helpful but the information obtained from the UN tests are more important to characterise the specific properties of a substance under different conditions.
Die Technische Regel für Anlagensicherheit (TRAS) 410 mit
dem Titel Erkennen und Beherrschen exothermer Reaktionen
stellt im Rahmen der Betrachtung der thermischen
Prozesssicherheit eine Anleitung zur systematischen Erarbeitung
von Gefahren bei chemischen Stoffumwandlungen
im Industriemaßstab dar. Sie unterstützt bei der Bewertung
der Gefahren und bei der Erstellung von Maßnahmen, um
Störfälle zu verhindern. Am Beispiel der exotherm ablaufenden
Synthese von tert.-Butylperoxypivalat, einem organischen
Peroxid, wird die Vorgehensweise dargestellt. Organische
Peroxide sind als thermisch instabile Verbindungen bekannt
und besitzen dadurch ein zusätzliches Gefahrenpotential.
Die Technische Regel für Anlagensicherheit (TRAS) 410 mit
dem Titel "Erkennen und Beherrschen exothermer Reaktionen"
stellt im Rahmen der Betrachtung der thermischen
Prozesssicherheit eine Anleitung zur systematischen Erarbeitung
von Gefahren bei chemischen Stoffumwandlungen
im Industriemaßstab dar. Sie unterstützt bei der Bewertung
der Gefahren und bei der Erstellung von Maßnahmen, um
Störfälle zu verhindern. Am Beispiel der exotherm ablaufenden
Synthese von tert.-Butylperoxypivalat, einem organischen
Peroxid, wird die Vorgehensweise dargestellt. Organische
Peroxide sind als thermisch instabile Verbindungen bekannt
und besitzen dadurch ein zusätzliches Gefahrenpotential.
The explosive properties of mixtures of aqueous hydrogen peroxide (H2O2) and different alcohols (ROH) like 2-propanol (2-PropOH), 2-methyl-2-propanol (TBA), 2-methyl-2-butanol (TAA) and 2-methyl-2-pentanol (THA) were investigated. Among others, the potential hazard of such mixtures may be characterized by their ability to react by different mechanisms of an explosion in the condensed phase, e.g. the thermal explosion or the detonation. Accordingly, the mixtures were experimentally investigated either by heating them up under confinement in different autoclaves or by exposing them to a shock wave impact applying the steel tube test. The results are discussed and compared to literature data.
A closed pressure vessel test (CPVT) screen for explosive properties of energetic organic compounds
(2007)
Results of a round-robin test on a mini-autoclave are reported and previously proposed criteria reviewed. Criteria based upon the results for three standard materials are now put forward. These standards-based criteria, in contrast to numerical criteria, theoretically allow any laboratory to utilize the data accumulated to date, irrespective of the equipment used. The practical requirement is that adequate discrimination can be achieved. Data to assess this are given.
Exothermic reactions involving organic peroxides carry a high potential hazard and must be considered with care. A safe handling requires, among others, the assessment of thermal process safety, for which safety characteristics like overall heat production and the resulting adiabatic temperature rise are essential. The article presents the results of the calorimetric investigation of the synthesis of four peroxycarboxylic esters, three tert-Butyl and one tert-Amyl peroxycarboxylic ester. In the two-step synthesis the second one clearly shows the higher exothermic potential. The overall heat production lies in the range of 126135 kJ/mol and is nearly independent of the carboxylic acid residual in the tert-Butyl peroxycarboxylic ester. The calculated adiabatic temperature rise is 7080 K. Influence of temperature and feed rate on the heat generation is discussed for one species. A grading of the synthesis with respect to temperature levels according to the criticality classes by Stoessel leads to the most critical for an exothermic reaction.
Mini Closed Pressure Vessel Test - An applicable test equipment for high energetic materials?
(2015)
Für die Bestimmung der SADT existieren verschiedene Prüfverfahren, die einen Zeitaufwand von mindestens einem Tag bis zu mehreren Wochen erfordern. Es ist deshalb wünschenswert, bereits in einem frühen Stadium von sicherheitstechnischen Untersuchungen die SADT ohne großen zeitlichen Aufwand zu bestimmen bzw. abzuschätzen. Ein klassisches Screening-Verfahren, um Stoffe mit geringem Material- und Zeitaufwand zu charakterisieren ist die Diffenrtial Scanning Calorimetry (DSC). Wie aus der Literatur bekannt, kann bei Anwendung eines definierten Kriteriums für die Bestimmung der Onset-Temperatur in der DSC eine SADT berechnet werden, die im Vergleich zum experimentell bestimmten Wert geringe Abweichungen besitzt. Diese Methodik wird für weitere flüssige und neu für feste organische Peroxide angewendet. Im Ergebnis zeigt sich unter Berücksichtigung eines zusätzlichen Sicherheitsabstandes von 5 K bis auf eine Ausnahme ein gutes Abbild der gemessenen SADT.
A major item of thermal process safety, concerning the industrial realisation of exothermic reactions, is the determination of a temperature, where a reaction can be carried out without risk for humans, environment, and of economic loss. The so-called limit temperature Texo is a safety parameter for the reaction process and should not be mixed up with the Self Accelerating Decomposition Temperature (SADT). The last one refers to a temperature value for safe transportation including specific conditions like transport time and type of containment.
In Germany a technical guide (Identification and Control of Exothermic Chemical Reactions, TRAS 410, 2012) specifies three approaches for determining Texo. In this work, all these approaches were applied to specify Texo for the synthesis of three tert-Butyl peroxycarboxylic esters. Peroxycarboxylic esters are a subdivision of organic peroxides, known for their high hazardous potential.
Results differed partly significant. Anyhow, all of the used techniques and evaluation methods led to Texo values, which were on the safe side – taken the Texo value estimated by the heat release criterion as reference. This method is considered by the authors as a very accurate one.
Organic peroxides are known for their decomposition behaviour and for considerable heat release connected with pressure build up. Efforts are required to run the industrial synthesis in semi-batch mode on safe condition. With the aim to use advantages as good heat transfer and small hold up, the synthesis of a peroxycarboxylic ester, namely tert-Butyl peroxy-2-ethylhexanoate (TBPEH), was transformed into continuous mode using a tube reactor with inner dimension of 1 mm. An appraisal of the critical diameter of the tube was done in advance. The use of an ultrasonic device allowed for specific reaction parameters a nearly complete conversion of the educts.
Topic of the presentation is the predictability of safety characteristics like the Self Accelerating Decomposition Temperature (SADT) by means of simple correlations from DSC measurements or by models, which incorporate amongst others the molecular structure of the considered compound.
Already existing models of quantitative structure-property relationship (QSPR) for SADT determination suffer from test results, which are, on the majority, not comprehensible. The quality of the generated models is questionable.
One item within the Safera-project is the provision of reliable data to have a solid basis for the prediction.
Autoclave methods are commonly used when pressure progress under thermal stress is of interest. One of them is the mini-autoclave method by Kühner AG. To test the robustness of the equipment under powerful exposure, two known high energetic materials, DNT and TNT, were investigated. The sample mass was increased stepwise in the range from 0.25 g to 1.0 g. For one test (1 g TNT), gas burners instead of the usually employed 2-zone heating block, were used to intensify the test conditions. Results showed the expected slower pressure generation of DNT in comparison to TNT. The mechanical robustness of the apparatus could be approved in all runs. Pressure data were used to calculate the energy release of decomposition. The values were in good agreement with the heat of decomposition, estimated by DSC.
This paper gives a brief overview of the findings of hexachlorobenzene (HCB) in fireworks compositions observed within EC type-examinations according to Module B (as set out in the annex II of the Directive 2007/23/EC) of the notified body BAM. In this work, roughly 220 samples were analysed, originating from 49 consumer fireworks articles of the category F2, such as batteries, combinations, fountains and rockets. It was found that the vast majority of samples showed concentrations below 5 mg HCB/kg. However, in three cases concentration values between 5 mg HCB/kg and 50 mg HCB/kg werre observed, and in a further four cases extreme values of up to 8046 mg HCB/kg were detected. The results of this study are compared with published HCB findings originating from market surveillance activities in Europe.
Exotherme Reaktionen verursachten in der Vergangenheit im industriellen Maßstab immer wieder Unfälle. Deshalb ist die Kenntnis des Gefahrenpotentials einer chemischen Reaktion sowohl im Normalbetrieb als auch bei Abweichungen davon eine Voraussetzung für eine sichere Prozessführung. Mit der Veröffentlichung der Technischen Regel für Anlagensicherheit (TRAS) 410 "Erkennen und Beherrschen exothermer Reaktionen" im Jahr 2001 existiert für chemische Stoffumwandlungen im Industriemaßstab eine auf dem Stand der Sicherheitstechnik basierende Anleitung zur systematischen Identifizierung von Gefahren, zu deren Bewertung und zur Erstellung von Maßnahmen, um Störfälle zu verhindern. Betrachtet wird dabei vorrangig die thermische Prozess-Sicherheit. Ein erhöhtes Gefahrenpotential besitzen exotherme Reaktionen an denen wie im vorliegenden Fall organische Peroxide beteiligt sind. Diese Verbindungsgruppe ist für ihre thermische Instabilität bekannt. In dieser Arbeit wird die unter basischen Bedingungen, zweistufig ablaufende Umsetzung von tert.-Butylhydroperoxid (TBHP) mit Pivaloylchlorid zum tert.-Butylperoxypivalat (TBPP) untersucht. TBHP, das auftretende Zwischenprodukt und TBPP gehören zur Stoffgruppe der organischen Peroxide. Bei der Bewertung der thermischen Prozess-Sicherheit der TBPP-Synthese wurde entsprechend der TRAS 410 vorgegangen. Die thermische Stabilität der beteiligten Stoffe wurde mit thermoanalytischen Screening-Methoden untersucht und die Reaktion durch kalorimetrische Untersuchungen charakterisiert. Die formale Anwendung der 100 K-Regel zur Festlegung der Grenztemperatur Texo, bei der alle an der Reaktion beteiligten Stoffe unter Verfahrensbedingungen sicher handhabbar sind, beträgt -36 °C. Bei dieser Temperatur ist der Prozess nicht durchführbar, da einzelne Reaktionskomponenten auskristallisieren und die Reaktion nicht wie gewünscht stattfinden kann. Anhand zusätzlicher Untersuchungsergebnisse zur Zersetzungskinetik des Produktes wird erläutert, dass im vorliegenden Fall von der o. g. Regel abgewichen werden kann. Als minimale Prozesstemperatur wurden 0 °C und als maximale Prozesstemperatur 20 °C festgelegt. Der Normalbetrieb wird im Rahmen der festgelegten Verfahrensparameter als sicher bewertet. Die Reaktion läuft dosierkontrolliert ab, eine Akkumulation tritt nicht auf. Aufgrund der geringen Differenz zwischen maximaler Prozesstemperatur und Onset-Temperatur der Zersetzung, besteht bei geringen Abweichungen vom Normalbetrieb die Gefahr, die unkontrollierte Zersetzung des Produktes einzuleiten. Temperaturanstieg und Gasproduktion führen zum Überschreiten der Auslegungsparameter der Anlage. Um die Reaktion durchführen zu können, müssen unbedingt vorbeugende als auch auswirkungsbegrenzende Maßnahmen getroffen werden. Abschließend wird mit Hilfe dimensionsloser Kenngrößen die Maßstabsübertragung mit dem Ziel vorgenommen, Grenzen für Reaktionsvolumina und Dosierzeiten festzulegen.
For the industrial production of chemicals a safe process design is required to avoid harm to people and
environment. It becomes tremendous important if one or more of the following points are characteristic for
the synthesis: high heat release, explosive atmosphere, presence of toxic and/or of thermal unstable substances.
One substance group, known for being unstable, is the group of organic peroxides. They are potential
high energetic substances. Many syntheses of organic peroxides are carried out in semi-batch
mode to control the heat release in a good manner. With the aim to increase process control, the advantages
of continuous reaction mode, combined with micro reaction technology, are used for the synthesis
of one specific organic peroxide in this work.
This approach is not only characterised by shorter residence time, good heat transfer, but also by smaller
quantities of managed chemicals, and, therefore, by a lower hazard potential. Often yield and selectivity
can be improved additionally.
For the study a peroxyester, namely tert-Butyl peroxy-2-ethylhexanoate (TBPEH), with known thermal
hazard potential was chosen. The two phase liquid/liquid reaction was carried out in three types of reactors.
A small scale tubular reactor, stressed by ultrasound, and two different micro structured reactors were
used. One of them had a meandering and the other a split-and-recombine channel structure. Synthesis
temperature was also varied.
From preliminary studies it was known that the side reaction of the involved carboxylic acid chloride to the
corresponding acid can become more important in continuous mode compared to semi-batch mode. The
effect of reactor type and temperature on selectivity and therefore yield of TBPEH was analysed and compared.
In result the reaction could be carried out in a safe manner. The high heat-exchanging efficiency of the
used reactors and the short residence time allowed synthesis temperature near the onset temperature of
decomposition of TBPEH. In relation to the results of the capillary tube and of the reactor with meandering
channel structure (MR), the results for the split-and-recombine reactor (SAR) showed the best trend line.
Further studies have to underline the result. Compared to the traditional reaction path (the semi-batch
mode), a higher space time yield could be achieved. This promising information is accompanied by the fact
of low reaction volumes. In consequence the productivity is low without a numbering up of reaction channels
or a scaling up of it. The nowadays existing philosophy of producing a specific quantity of product by a
company, followed by the transport to the costumer may change. Just organic peroxides, used in small
quantities, e.g. as initiators for polymerisation processes or as resin hardeners, provide the opportunity for
an on-demand-production.
The synthesis of peroxycarboxylic esters, as one subgroup of organic peroxides, is characterized by a high thermal hazard potential regarding process safety. In case of failure in the production process, e.g., if the heat of reaction cannot be removed sufficiently fast, decomposition reactions can be triggered, and as a result, remarkable amounts of heat and gas can be released and can cause a high extent of damage. Multifarious technical and organizational measures are necessary to ensure the safe industrial production of peroxides. With the introduction of microreaction technology plenty of possibilities have been opened to carry out highly exothermic reactions in smaller volumes and with more efficient heat removal. In this paper we report the application of three different microstructured reactors, representing different mixing strategies, to synthesize two peroxymonocarboxylic esters, namely tert-butyl peroxypivalate and tert-butyl peroxy-2- thylhexanoate. The following reactor types were considered: an orifice microreactor, a split and recombine microreactor and a capillary tube reactor in combination with ultrasonication. The efficiency of the two Phase liquid/liquid reaction is expressed in comparison of conversion and selectivity. With microreaction technology a remarkable increase in space-time-yield, ranging from 12,500 kg·m−3·h−1 to 414,000 kg·m−3·h−1, is achieved.
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.
Self-reactive substances are unstable chemical substances which can easily decompose and may lead to explosion in transport, storage, or process situations. For this reason, their thermal stability properties are required to assess possible process safety issues and for classification purpose. In this study, the first quantitative structure–property relationships (QSPR) dedicated to this class of compounds were developed to predict the heat of decomposition of possible self-reactive substances from their molecular structures. The database used to develop and validate the models was issued from a dedicated experimental campaign on 50 samples using differential scanning calorimetry in homogeneous experimental conditions. QSPR models were derived using the GA-MLR methods (using a genetic algorithm and multi-linear regressions) using molecular descriptors calculated by Dragon software based on two types of inputs: 3D molecular structures determined using the density functional theory (DFT), allowing access to three-dimensional descriptors, and from SMILES codes, favoring the access to simpler models, requiring no preliminary quantum chemical calculations. All models respected the OECD validation guidelines for regulatory ac
ceptability of QSPR models. They were tested by internal and external validation tests and their applicability domains were defined and analyzed.
Mit dem Handbuch für Prüfungen und Kriterien bezeichnet) wird das Klassifizierungsschema der Vereinten Nationen (UN) für gefährliche Güter im Rahmen der Beförderungsvorschriften und für gefährliche Stoffe und Gemische gemäß GHS (Globally Harmonized System of Classification and Labelling of Chemicals) beschrieben. Außerdem enthält es eine Beschreibung der als am geeignetsten angesehenen Prüfmethoden und -verfahren, welche dem "Klassifizierenden" die notwendigen Informationen für eine korrekte Einstufung liefern. Der Begriff "Klassifizierender" wird im gesamten Handbuch allgemein verwendet, um die Stelle anzugeben, die die Klassifizierung vornimmt. Für einige Reglungsbereiche kann dieses eine speziell zuständige Behörde oder eine benannte Prüfbehörde sein, in einem anderen Reglungsbereich, soweit es zulässig ist, kann es auch die Selbsteinstufung durch den Hersteller oder Lieferanten bedeuten. Der jeweilige Reglungsbereich sollte beim Auftreten dieses Begriffes berücksichtigt werden, um die für die Klassifizierung verantwortliche Stelle korrekt zu identifizieren.