TY - CONF A1 - Wehrstedt, Klaus-Dieter A1 - Knorr, Annett T1 - Miniautoclave - test results on organic peroxides and self-reactive substances T2 - Energetic and Oxidising Substances (EOS) working group meeting CY - Washington, DC, USA DA - 2001-03-12 PY - 2001 AN - OPUS4-1509 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Wehrstedt, Klaus-Dieter T1 - Miniautoklav - Screening-Verfahren für organische Peroxide und selbstzersetzliche Stoffe? T2 - Vortrag bei der Firma Peroxid-Chemie GmbH & Co. KG CY - Pullach im Isartal, Germany DA - 2001-11-13 PY - 2001 AN - OPUS4-1510 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schreck, Andreas A1 - Knorr, Annett A1 - Wehrstedt, Klaus-Dieter A1 - Gmeinwieser, T. A1 - Steinbach, J. T1 - Sicherheitstechnische Untersuchungen zur Alkylierung von Wasserstoffperoxid mit verschiedenen Alkoholen T2 - 34. Sitzung des DECHEMA-Arbeitsausschusses "Sicherheitstechnische Kenngrößen" CY - Frankfurt am Main, Deutschland DA - 2001-05-17 PY - 2001 VL - 34 AN - OPUS4-1512 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wehrstedt, Klaus-Dieter A1 - Knorr, Annett A1 - Schreck, Andreas T1 - Test results on energetic substances using the Miniautoclave T2 - Energetic and Oxidising Substances (EOS) working group meeting CY - Buxton, England, UK DA - 2000-04-10 PY - 2000 AN - OPUS4-1518 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wehrstedt, Klaus-Dieter A1 - Knorr, Annett T1 - Miniautoclave - test results on organic peroxides and self-reactive substances T2 - Energetic and Oxidising Substances (EOS) ad hoc group meeting CY - Tsukuba, Japan DA - 2000-11-13 PY - 2000 AN - OPUS4-1519 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Synthese organischer Perester T2 - DECHEMA Arbeitsausschuss "Reaktionstechnik sicherheitstechnisch schwieriger Prozesse" CY - Frankfurt am Main, Germany DA - 2002-03-07 PY - 2002 AN - OPUS4-3049 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schreck, Andreas A1 - Knorr, Annett A1 - Wehrstedt, Klaus-Dieter A1 - Wandrey, Peter-Andreas A1 - Gmeinwieser, T. A1 - Steinbach, J. T1 - Investigation of the explosive hazard of mixtures containing hydrogen peroxide and different alcohols N2 - The explosive properties of mixtures of aqueous hydrogen peroxide (H2O2) and different alcohols (R–OH) 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. KW - Mixtures of hydrogen peroxide and alcohols KW - Explosive properties KW - Steel tube test KW - TEVT KW - MCPVT PY - 2004 U6 - https://doi.org/10.1016/j.jhazmat.2004.01.003 SN - 0304-3894 VL - 108 IS - 1-2 SP - 1 EP - 7 PB - Elsevier CY - Amsterdam AN - OPUS4-3535 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wehrstedt, Klaus-Dieter A1 - Knorr, Annett A1 - Schuurman, P. T1 - The "Mini Closed Pressure Vessel Test (MCPVT)" as a screening or classification test for explosive properties of organic peroxides N2 - 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. KW - MCPVT KW - Organic peroxides KW - UN Manual of Tests and Criteria KW - Explosive properties PY - 2003 U6 - https://doi.org/10.1016/j.jlp.2003.08.001 SN - 0950-4230 SN - 1873-3352 VL - 16 SP - 523 EP - 531 PB - Butterworth CY - Guildford, Surrey AN - OPUS4-2699 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Anwendung der TRAS 410 auf die Sicherheitstechnische Beurteilung einer Perestersynthese T2 - Sicherheit von chemischen Reaktionen und Prozessen - Beherrschen von Reaktionen unter Druck; Fachseminar Mettler-Toledo CY - Frankfurt am Main, Germany DA - 2006-06-22 PY - 2006 AN - OPUS4-12499 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Schendler, Thomas T1 - Ermittlung von Kenngrößen zur Beurteilung von Gefahren durch exotherme chemische Reaktionen T2 - 7. Kolloquium zu Fragen der chemischen und physikalischen Sicherheitstechnik CY - Berlin, Germany DA - 1997-05-28 PY - 1997 AN - OPUS4-12704 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Fritzsche, Lutz A1 - Knorr, Annett T1 - Continuous synthesis of a high energetic substance using small scale reactors N2 - 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. T2 - ICheaP-11 - 11th International conference on chemical & process engineering CY - Milan, Italy DA - 2013-06-02 KW - Organic peroxide KW - Small scale reactor KW - Process safety KW - Continuous mode PY - 2013 SN - 978-88-95608-23-5 U6 - https://doi.org/10.3303/CET1332115 SN - 1974-9791 N1 - Serientitel: Chemical engineering transactions – Series title: Chemical engineering transactions IS - 32 SP - 685 EP - 690 PB - AIDIC, Associazione Italiana di Ingegneria Chimica CY - Milan AN - OPUS4-28730 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Fritzsche, Lutz T1 - Continuous Synthesis of a High Energetic Substance Using Small Scale Reactors T2 - 11th International Conference on Chemical and Process Engineering CY - Milan, Italy DA - 2013-06-02 PY - 2013 AN - OPUS4-28716 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Fritzsche, Lutz T1 - Transformation of the 2nd step of a perester synthesis from semi-batch to continuous mode T2 - 12th International Conference on Microreaction Chemistry CY - Lyon, France DA - 2012-02-20 PY - 2012 AN - OPUS4-26369 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Exotherme Reaktionen: Grundlagen der Wärmebilanz und Untersuchungsmethoden T2 - Seminar der BG RCI "Sicheres Betreiben chemischer Prozesse, Schwerpunkt: Exotherme Reaktionen" CY - Maikammer, Germany DA - 2011-11-07 PY - 2011 AN - OPUS4-24753 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Rockland, Ulrike A1 - Steinbach, J. T1 - Anwendung der TRAS 410 für die sicherheitstechnische Bewertung einer Perstersynthese bei Normalbetrieb T2 - DECHEMA/GVC-Jahrestagung 2003 CY - Mannheim, Germany DA - 2003-09-16 PY - 2003 AN - OPUS4-4689 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Rockland, Ulrike A1 - Steinbach, J. T1 - Sicherheitstechnische Bewertung nach der TRAS 410 am Beispiel einer Perestersynthese N2 - 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. T2 - 10. Kolloquium zu Fragen der chemischen und physikalischen Sicherheitstechnik, BAM CY - Berlin, Germany DA - 2004-06-17 PY - 2004 AN - OPUS4-4849 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Rockland, Ulrike A1 - Steinbach, J. ED - Rockland, U. T1 - Sicherheitstechnische Bewertung nach der TRAS 410 am Beispiel einer Perestersynthese N2 - 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. T2 - 10. Kolloquium zu Fragen der chemischen und physikalischen Sicherheitstechnik CY - Berlin, Deutschland DA - 2004-06-17 PY - 2004 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-48504 SP - 43 EP - 48 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-4850 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Sichere Führung exothermer chemischer Reaktionen, Grundlagen T2 - BG-Chemie-Seminar: Sicheres Betreiben chemischer Prozesse, Schwerpunkt exotherme Reaktionen CY - Maikammer, Germany DA - 2007-11-26 PY - 2007 AN - OPUS4-16237 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Knorr, Annett A1 - Koseki, H. A1 - Li, X.-R. A1 - Tamura, M. A1 - Wehrstedt, Klaus-Dieter A1 - Whitmore, M. W. T1 - A closed pressure vessel test (CPVT) screen for explosive properties of energetic organic compounds N2 - 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. KW - Closed pressure vessel test KW - Mini-autoclave KW - MCPVT KW - Explosive properties PY - 2007 SN - 0950-4230 SN - 1873-3352 VL - 20 IS - 1 SP - 1 EP - 6 PB - Butterworth CY - Guildford, Surrey AN - OPUS4-14385 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Arbeitsgebiete der Gruppe "Sichere Reaktionsführung" T2 - Sitzung Dechema AA "Reaktionstechnik sicherheitstechnisch schwieriger Prozesse" CY - Frankfurt am Main, Germany DA - 2007-03-14 PY - 2007 AN - OPUS4-14779 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Sicherheitstechnische Beurteilung einer exothermen chemischen Reaktion, Schwerpunkt Thermische Prozesssicherheit T2 - Seminar an der TU Chemnitz, Bereich Technische Chemie (Prof. Klemm) CY - Chemnitz, Germany DA - 2008-05-09 PY - 2008 AN - OPUS4-17834 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fritzsche, Lutz A1 - Knorr, Annett T1 - Transformation of the 2nd step of a peroxyester synthesis from semi-batch to continuous mode N2 - 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. KW - Organic peroxide KW - Tubular reactor KW - Process safety KW - Continuous mode KW - Ultrasound PY - 2013 U6 - https://doi.org/10.1016/j.cep.2013.03.019 SN - 0255-2701 VL - 70 SP - 217 EP - 221 PB - Elsevier CY - Lausanne AN - OPUS4-28937 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Exotherme chemische Reaktionen: Grundlagen der Wärmebilanz und Untersuchungsmethoden T2 - Seminar der BG RCI "Sicheres Betreiben chemischer Prozesse, Schwerpunkt Exotherme Reaktionen" CY - Maikammer, Germany DA - 2010-11-08 PY - 2010 AN - OPUS4-22368 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Wirker, Ringo A1 - Antes, Jürgen T1 - Orts- und zeitaufgelöste Wärmestrommessung in einem mikrostrukturierten Fallfilmreaktor T2 - 19. Ulm-Freiberger Kalorimetrietage CY - Freiberg, Germany DA - 2011-03-16 PY - 2011 AN - OPUS4-23573 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Synthese einer hochenergetischen Substanz mittels kontinuierlicher Reaktionsführung T2 - Erfahrungsaustausch: Sonochemie in Mikroreaktoren CY - Rostock, Germany DA - 2012-05-10 PY - 2012 AN - OPUS4-25854 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Guillaume, F. A1 - Knorr, Annett A1 - Rotureau, P. T1 - First QSPR models to predict the thermal stability of potential self-reactive substances N2 - 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. KW - Self-reactive substances KW - Quantitative Structure-Property Relationships KW - Thermal stability KW - Genetic algorithm PY - 2022 U6 - https://doi.org/10.1016/j.psep.2022.05.017 SN - 0957-5820 VL - 163 SP - 191 EP - 199 PB - Elsevier Ltd. AN - OPUS4-55631 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schwarz, Silke A1 - Knorr, Annett A1 - Lohrer, Christian T1 - Screening of hexachlorobenzene (HCB) contents in fireworks N2 - 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. KW - Consumer fireworks KW - Forbidden substances KW - Pyrotechnic articles PY - 2014 SN - 1082-3999 IS - 33 SP - Article 0103, 3 EP - 8 CY - Whitewater, Colo. AN - OPUS4-30758 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Fritzsche, Lutz T1 - Specification of the Limit Temperature Texo for a Peroxide Synthesis Using Different Estimation Methods T2 - CISAP6, 6th International Conference on Safety & Environment in Process & Power Industry CY - Bologna, Italy DA - 2014-04-13 PY - 2014 AN - OPUS4-30694 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Fritzsche, Lutz T1 - 2-Phasenreaktion in mikrostrukturierten Reaktoren T2 - Dechema Jahrestreffen Reaktionstechnik CY - Würzburg, Germany DA - 2014-04-28 PY - 2014 AN - OPUS4-30696 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Fritzsche, Lutz A1 - Knorr, Annett ED - Cozzani, V. ED - de Rademaeker, E. T1 - Specification of the limit temperature Texo for a peroxide synthesis using different estimation methods N2 - 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. T2 - CISAP-6 - 6th International Conference on Safety and Environment CY - Bologna, Italy DA - 13.04.2014 KW - Peroxide KW - TRAS410 KW - Process safety PY - 2014 SN - 978-88-95608-27-3 U6 - https://doi.org/10.3303/CET1436021 SN - 2283-9216 N1 - Serientitel: Chemical engineering transactions – Series title: Chemical engineering transactions IS - 36 SP - 121 EP - 126 PB - AIDIC, Associazione Italiana di Ingegneria Chimica CY - Milano AN - OPUS4-30618 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Wirker, Ringo A1 - Fritzsche, Lutz A1 - Gegenheimer, M. A1 - Antes, Jürgen T1 - Kalorimetrische Untersuchung einer Ozonolysereaktion im Mikro-Fallfilmreaktor T2 - 9. Fachtagung "Anlagen-, Arbeits- und Umweltsicherheit" CY - Köthen, Germany DA - 2008-11-06 PY - 2008 AN - OPUS4-18991 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Wirker, Ringo A1 - Klemm, E. A1 - Löb, D. A1 - Franke, R. T1 - Einsatz der Mikroreaktionstechnik bei der Übertragung einer 2-stufigen exothermen Gas-/Flüssigphasenreaktion vom Semibatch - in den kontinuierlichen Betrieb T2 - 9. Fachtagung "Anlagen-, Arbeits- und Umweltsicherheit" CY - Köthen, Germany DA - 2008-11-06 PY - 2008 AN - OPUS4-18931 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fritzsche, Lutz A1 - Knorr, Annett T1 - Calorimetric study of peroxycarboxylic ester synthesis N2 - 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 126–135 kJ/mol and is nearly independent of the carboxylic acid residual in the tert-Butyl peroxycarboxylic ester. The calculated adiabatic temperature rise is 70–80 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. KW - Reaction calorimetry KW - Organic peroxide KW - Peroxycarboxylic ester KW - Process safety PY - 2009 U6 - https://doi.org/10.1016/jhazmat.2008.07.032 SN - 0304-3894 VL - 163 IS - 2-3 SP - 1403 EP - 1407 PB - Elsevier CY - Amsterdam AN - OPUS4-18943 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Mini closed pressure vessel test - a systematic approach T2 - Workshop "Result transfer of safety - related investigations from bench to pilot scale CY - Södertälje, Sweden DA - 2009-01-23 PY - 2009 AN - OPUS4-18933 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Vorgehensweise bei der Bestimmung und Bewertung des thermischen Gefahrenpotenziales chemischer exothermer Reaktionen T2 - Seminarreihe, TU Stuttgart, Institut für Technische Chemie CY - Stuttgart, Germany DA - 2009-10-20 PY - 2009 AN - OPUS4-20321 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett T1 - Exotherme chemische Reaktionen: Grundlagen der Wärmebilanz und Untersuchungsmethoden T2 - BG Chemie Seminar "Sicheres Betreiben chemischer Prozesse, Schwerpunkt Exotherme Reaktionen" CY - Maikammer, Germany DA - 2009-10-07 PY - 2009 AN - OPUS4-20322 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Wirker, Ringo T1 - Ozonolyse im konventionellen Semibatch-Reaktor und im mikrostrukturierten Fallfilmreaktor T2 - ProcessNet AA "Reaktionstechnik sicherheitstechnisch schwieriger Prozesse" - Sitzung CY - Frankfurt am Main, Germany DA - 2009-10-22 PY - 2009 AN - OPUS4-20325 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Knorr, Annett A1 - Fayet, G. A1 - Rotureau, P. A1 - Wehrstedt, Klaus-Dieter T1 - Predictive Methods for Determining the Thermal Decomposition Properties of Hazardous Substances N2 - 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. KW - QSPR KW - HAZPRED KW - Organic peroxides KW - Self-reactive substances PY - 2019 UR - https://www.aidic.it/ U6 - https://doi.org/10.3303/CET1977057 SN - 2283-9216 VL - 77 SP - 337 EP - 342 PB - AIDIC CY - Milano AN - OPUS4-51282 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Illg, T. A1 - Knorr, Annett A1 - Fritzsche, Lutz T1 - Microreactors - a powerful tool to synthesize peroxycarboxylic esters N2 - 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. KW - Microreactor KW - Peroxide KW - Continuous processing KW - Process safety KW - Flow chemistry PY - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-352496 SN - 1420-3049 VL - 21 IS - 1 SP - Article 5, 1 EP - 16 PB - MDPI CY - Basel AN - OPUS4-35249 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Krebs, Holger A1 - Wehrstedt, Klaus-Dieter T1 - Mini Closed Pressure Vessel Test - An applicable test equipment for high energetic materials? T2 - IGUS Energetic and Oxidising Substances (EOS) Working Group Meeting CY - Ottawa, Canada DA - 2015-05-06 PY - 2015 AN - OPUS4-33479 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - THES A1 - Knorr, Annett T1 - Anwendung der TRAS 410 auf die sicherheitstechnische Beurteilung einer Perestersynthese T1 - Application of the technical rule TRAS 410 to the safety evaluation of a peroxide synthesis N2 - 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. N2 - In the past exothermic reactions in the industrial scale were repeatedly the cause of accidents. Therefore the knowledge of the potential hazards of an exothermic reaction for normal operations as well as for deviations is a precondition for a safe handling of the industrial process. With the release of the technical guide for identification and control of exothermic chemical reactions (“Technische Regel für Anlagensicherheit 410, Erkennen und Beherrschen exothermer chemischer Reaktionen (TRAS 410)“) in Germany 2001 there is a tool available, which is based on the art of safety engineering helps, to identify and to assess hazards and to derive measures to prevent failures. The main focus is pointed to the thermal process safety. A higher potential hazard possess exothermic reactions, in which, like in the present case, organic peroxides are involved. These type of compounds are well known for their thermal instability. In the thesis a two-phase, semi-batch reaction of tert-Butylhydroperoxide (TBHP) with pivaloyl chloride to tert-Butylperoxypivalate (TBPP) was investigated. Both TBHP, the formed intermediate and TBPP belong to the group of peroxide. The technical guide TRAS 410 was applied to assess the thermal process safety of the TBPP synthesis. The thermal stability of the involved substances was examined with screening methods and the reaction itself was characterised by calorimetric measurements. The technical application of the 100-Kelvin rule led to a limit temperature Texo of -36 °C, where a safe handling of all substances is firmed. Practically the process is not realisable at this temperature. Due to additionally studies and the determination of the activation energy and the Arrhenius factor of the decomposition of TBPP the lowest process temperature was set at 0 °C. As maximum temperature 20 °C was fixed. In line with the defined operating conditions the normal mode is assessed to be safe. The reaction is controlled by the feed velocity. No accumulation appeared. Because of a narrow gap between process temperature and the temperature, were the decomposition of TBPP starts considerably, only small deviations of process conditions are permitted. Otherwise the decomposition will run uncontrolled with temperature raise and gas production, definitely resulting in exceeding design limits of the process. To carry out the process several preventive measures like control engineering techniques have to be installed. Finally scale-up using dimensionless parameter is done to determine minimum and maximum reaction volume and feed time. KW - Maßstabsübertragung KW - Peroxidsynthese KW - Reaktionskalorimetrie KW - Semibatch-Reaktion KW - Sicherheit KW - Peroxide synthesis KW - Reaction calorimetry KW - Safety KW - Scale-up KW - Semibatch reaction PY - 2006 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:83-opus-11954 SP - 1 EP - 162 PB - Technische Universität CY - Berlin AN - OPUS4-35406 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Knorr, Annett A1 - Krebs, Holger T1 - Testing of DNT and TNT by the mini-autoclave method N2 - 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. KW - Autoclave KW - DNT KW - TNT KW - Decomposition KW - Energy PY - 2014 U6 - https://doi.org/10.1002/prep.201300090 SN - 0721-3115 SN - 0340-7462 SN - 1521-4087 VL - 39 IS - 4 SP - 580 EP - 585 PB - Wiley-VCH CY - Weinheim AN - OPUS4-31207 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Wehrstedt, Klaus-Dieter A1 - Lünne, Mario T1 - Prediction of SADT – requirements for simple and complex correlations N2 - 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. T2 - Safera-Workshop "Predictive methods for determining the decomposition properties of hazardous substances" CY - Ostrava, Czech Republic DA - 23.11.2016 KW - SADT KW - Prediction methods PY - 2016 AN - OPUS4-40192 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Knorr, Annett A1 - Lünne, M. A1 - Wehrstedt, Klaus-Dieter T1 - Vorhersage der selbstbeschleunigenden Zersetzungstemperatur (SADT) für organische Peroxide N2 - 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. T2 - 22. Kalorimetrietage CY - Braunschweig, Germany DA - 07.06.2017 KW - SADT KW - DSC PY - 2017 AN - OPUS4-41982 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Michael-Schulz, Heike A1 - Knorr, Annett A1 - Krischok, Frank A1 - Adebahr-Lindner, Yvonne A1 - Kelle, Frank A1 - Kamberi, Tevide A1 - Mudlaff, Sabine T1 - Empfehlungen für die Beförderung gefährlicher Güter - Handbuch über Prüfungen und Kriterien N2 - 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. KW - UN-Prüfmethoden KW - Gefahrstoffe KW - Einstufung KW - Klassifizierung KW - Verfahren PY - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-573175 SN - 978-3-9818564-5-3 SP - i EP - 649 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin ET - 7., Amd. 1 AN - OPUS4-57317 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -