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 - 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 - 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 - 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 - 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 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 - 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 - 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 - 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 -