TY - JOUR A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Mishra, K. B. A1 - Steinbach, J. T1 - The capability of commercial CFD code to predict organic peroxide fireball characteristics JF - Journal of Hazardous Materials N2 - Fireballs of liquid organic peroxides differ from those of liquid hydrocarbon fuels. Modified equations for predicting the fireball diameter, height, surface emissive power and the duration in dependence of the fuel mass are presented for di-tert-butyl peroxide. They base on 13 steel drum tests with fuel masses from 10 kg to 168 kg. Moreover, computational fluid dynamics simulations are performed using the laminar flamelet approach and a statistically turbulence treatment. Fireballs involving peroxide from 10 kg to 80 kg were simulated and their properties compared to the experimentally developed models. The deviations of each property are partially compensating each other leading to an adequate prediction of thermal safety distances for both, a time-independent and a time-averaged treatment. Simulations prove to be a good tool for predicting thermal radiation hazards of fireball scenarios. KW - Fireball KW - CFD simulation KW - Organic peroxide KW - Fire safety KW - DTBP PY - 2019 DO - https://doi.org/10.1016/j.jhazmat.2018.11.011 SN - 0304-3894 SN - 1873-3336 VL - 365 SP - 386 EP - 394 PB - Elsevier AN - OPUS4-47054 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wehrstedt, Klaus-Dieter A1 - Blankenhagel, Paul T1 - Organic peroxide fireballs - Report of progress N2 - 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. T2 - IGUS EOS Meeting CY - Shanghai, China DA - 09.04.2018 KW - Fireball KW - Organic peroxide KW - Thermal radiation KW - Safety distances PY - 2018 AN - OPUS4-45276 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Steinbach, J. A1 - Mishra, K. B. T1 - Thermal radiation assessment of fireballs using infrared camera JF - Journal of Loss Prevention in the Process Industries N2 - The thermal radiation impact of organic peroxide fireballs is experimentally assessed using an infrared camera. Fireballs are generated while liquid peroxide filled steel drums are subjected to gas burner fire at different heating rates. Three large burning clouds are observed with varying flame characteristics. Thermal radiation properties are assessed by infrared images with the presented methods. Despite of the two-dimensional temperature fields, the flames are treated and characterized as three-dimensional objects. Fireball diameters and heights are calculated based on a representing radiating sphere with the same cloud volume. By the use of the solid flame model and assumptions for emissivity and transmissivity, heat fluxes and thermal radiation doses against distance are predicted. Thermal safety distances are presented based on the maximum irradiance and the allowed exposure time. The validation of the maximum and time-dependent radiation fields is achieved through heat flux sensors in varying distances to the fireball. The results prove the use of an infrared camera and a volume based size calculation to fully assess the thermal radiation hazards of fireballs. KW - Fireball KW - Thermal radiation KW - Infrared camera KW - Organic peroxide KW - Safety distances PY - 2018 DO - https://doi.org/10.1016/j.jlp.2018.04.008 SN - 0950-4230 VL - 54 SP - 246 EP - 253 PB - Elsevier AN - OPUS4-45277 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Xu, S. A1 - Mishra, K. B. A1 - Steinbach, J. T1 - A new model for organic peroxide fireballs JF - Journal of Loss Prevention in the Process Industries N2 - Organic peroxides are capable to form fireballs with explosive violence. Only fireball models for liquid hydrocarbon fuels are available for the assessment of the thermal radiation properties. Because the development of such fireballs usually differ from those of organic peroxides the properties need to be characterized by modified equations. In this study liquid organic peroxide fireballs from 16 kg to 155 kg substance masses are characterized and compared to selected existing correlations. Flame characteristics and irradiances are measured with infrared cameras and heat flux sensors. All fireballs are consequences of simulated worst case scenarios where filled steel drums are engulfed by fire with varying heat impact. The differences of the given semi-empirical equations and the presented experimental work are explained. A new model is proposed for organic peroxide fireballs by modifying the constants of the known equations. The thermal radiation impact and safety distances are calculated and compared. KW - Organic peroxide KW - Fireball KW - Thermal radiation KW - Safety distances PY - 2017 DO - https://doi.org/10.1016/j.jlp.2017.10.002 SN - 0950-4230 VL - 50 IS - Part A SP - 237 EP - 242 PB - Elsevier Science AN - OPUS4-43069 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter T1 - Fireballs of liquid organic peroxides - New large scale test results N2 - Summary of recent research activities at BAM concerning large scale fireballs of organic peroxides (OP). For the tests performed in Nanjing, China, the experimental setup and data aquisition is briefly shown and results are discussed compared with semi-empirical models. A new model is proposed for assessing OP fireballs. Thermal safety distances are calculated and compared for the three large tests. T2 - IGUS EOS ad-hoc meeting CY - Franfkurt am Main, Germany DA - 25.09.2017 KW - Fireball KW - Organic peroxide KW - Thermal radiation KW - Safety distances PY - 2017 AN - OPUS4-43055 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter T1 - Fireballs of liquid organic peroxides - research at BAM N2 - Summary of recent research activities at BAM concerning fireballs of organic peroxides. Experimental setup and data aquisition is briefly shown and results are discussed compared with semi-empirical models. Moreover, approaches for CFD simulation methods are presented. Finally, collaborative research of BAM and NUST (China) is shown as an example for future work. T2 - Presentation at Nanjing University of Science and Technology (NUST) CY - Nanjing, China DA - 19.05.2017 KW - Fireball KW - Organic peroxide KW - CFD simulation PY - 2017 AN - OPUS4-41916 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter T1 - Fireballs of liquid organic peroxides - recent research activities N2 - Fire and explosion hazards associated with storage and transportation of flammable materials have been a matter of great interest in the recent times. There are numerous studies on pool fires, BLEVEs and fireballs of hydrocarbon fuels, whereas BLEVEs and fireballs of organic peroxides (OP) were not investigated in detail yet. Recent research activities on OP fireballs are presented in terms of mass burning rates, substance temperatures and the formation of fireballs. Differences to existing correlations and their impact on hazard assessment is shown. Finally different approaches for CFD modeling are presented and compared. T2 - IGUS EOS Meeting CY - Rijswijk, The Netherlands DA - 24.04.2017 KW - Fireballs KW - Organic peroxide KW - Thermal radiation KW - CFD-simulation PY - 2017 AN - OPUS4-40191 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Mishra, K. B. A1 - Steinbach, J. T1 - Prediction of organic peroxide fireball characteristics using CFD simulation T2 - Proceedings of the 8th European Combustion Meeting 2017 N2 - Single and multiple fireballs of di-tert-butyl peroxide are numerically investigated using ANSYS CFX. Calculations contain varying inlet conditions, scale-adaptive shear stress turbulence modeling and one-step combustion reaction on a three-dimensional hexahedral mesh. Time-resolved flame temperatures, sizes and thermal radiation are compared to experimental results. There, fireballs were generated by fire engulfment of steel drums containing 200 l substance. After a vigorous burning, the remaining peroxide forms single and multiple fireballs involving 10 % to 20 % of the initial amount. The comparison of all simulations and two selected experiments show the special numerical treatment required for organic peroxides. Finally, the numerical predictions of irradiance in 30 m distance to the fire show a good agreement for both experiments. This proves the use of CFD as an appropriate method for thermal hazard assessment and the prediction of safety distances for organic peroxide fireballs. T2 - 8th European Combustion Meeting 2017 CY - Dubrovnik, Croatia DA - 18.04.2017 KW - Organic peroxide KW - DTBP KW - Fireball KW - Steel drum KW - Simulation PY - 2017 SN - 978-953-59504-1-7 AN - OPUS4-39992 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Mishra, K. B. A1 - Steinbach, J. T1 - Fireballs as a possible hazard scenario of organic peroxides in steel drums T2 - MBE Tagungsband 2017 N2 - To simulate a full fire engulfment during transportation or storage a closed removable head steel drum filled with 200 l Di-tert-butyl peroxide (DTBP) is subjected to a wood fire. Due to the enormous heat flux and the exothermic self-decomposition large flames arise and finally multiple fireballs occur. The fireballs consume up to 20 % of the total mass (20 % equals to 31 kg). They are characterized by high surface emissive power and large flames associated with high thermal radiation causing spontaneous ignition of objects in the surrounding. The measured sizes of the DTBP fireballs are smaller compared to the results of the general equations for hydrocarbon fireballs. Because these equations are recommended by the Health and Safety Executive (UK) to be applicable for organic peroxides explicit comparisons of DTBP with LPG, diesel and gasoline concerning the characteristics of fireballs are carried out. Also the burning time is compared and confirms a faster combustion of the peroxide. Moreover, the development of size and emissive power for DTBP and diesel fireballs are compared in a normalized graph. The results provide the assumption that new empirical models are required to be developed for hazard assessment of organic peroxide fireballs. T2 - 5. Brand- und Explosionsschutztage 2017 CY - Magdeburg, Germany DA - 23.03.2017 KW - Organic peroxide KW - DTBP KW - Fireball KW - Steel drum KW - Simulation PY - 2017 SN - 978-3-00-056201-3 DO - https://doi.org/10.978.300/0562013 VL - 2017 SP - 1 EP - 9 PB - Otto-von-Guericke-Universität CY - Magdeburg AN - OPUS4-39994 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Mishra, K. B. A1 - Steinbach, J. T1 - Fireballs as a possible hazard scenario of organic peroxides in steel drums N2 - To simulate a full fire engulfment during transportation or storage a closed removable head steel drum filled with 200 l Di-tert-butyl peroxide (DTBP) is subjected to a wood fire. Due to the enormous heat flux and the exothermic self-decomposition large flames arise and finally multiple fireballs occur. The fireballs consume up to 20 % of the total mass (20 % equals to 31 kg). They are characterized by high surface emissive power and large flames associated with high thermal radiation causing spontaneous ignition of objects in the surrounding. The measured sizes of the DTBP fireballs are smaller compared to the results of the general equations for hydrocarbon fireballs. Because these equations are recommended by the Health and Safety Executive (UK) to be applicable for organic peroxides explicit comparisons of DTBP with LPG, diesel and gasoline concerning the characteristics of fireballs are carried out. Also the burning time is compared and confirms a faster combustion of the peroxide. Moreover, the development of size and emissive power for DTBP and diesel fireballs are compared in a normalized graph. The results provide the assumption that new empirical models are required to be developed for hazard assessment of organic peroxide fireballs. T2 - 5. Magdeburger Brand- und Explosionsschutztage CY - Magdeburg, Germany DA - 23.03.2017 KW - Organic peroxide KW - DTBP KW - Fireball KW - Steel drum KW - Simulation PY - 2017 AN - OPUS4-39993 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Mishra, K. B. A1 - Steinbach, J. T1 - Prediction of organic peroxide fireball characteristics using CFD simulation N2 - Organic peroxides (OP) are thermally unstable and burn rapidly due to exothermic self-decomposition capabilities. Since fireballs can be formed under certain worst case conditions the understanding of burning phenomena and radiation characteristics need to be improved to prevent damage of humans and infrastructure. An appropriate method for real-scale Evaluation can be the use of CFD simulations with the objective of reducing time-consuming and costly outdoor experiments. T2 - 8th European Combustion Meeting 2017 CY - Dubronik, Croatia DA - 18.04.2017 KW - Organic peroxide KW - DTBP KW - Fireball KW - Steel drum KW - Simulation PY - 2017 AN - OPUS4-39991 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Blankenhagel, Paul A1 - Wehrstedt, Klaus-Dieter A1 - Mishra, K. B. A1 - Steinbach, J. T1 - Thermal radiation impact of DTBP fireballs N2 - The burning behaviour and thermal radiation of pool fires of organic peroxides (OP) have been studied by several authors in the past. It was shown that mass burning rates, flame temperatures and thus the Surface Emissive Power (SEP) of OP exceed to that of hydrocarbons considerably. These facts lead to further investigations of even dangerous worst case scenarios i.e. related to storage and transportation. A metal drum containing 200 l of DTBP (Di-tert-butyl peroxide) is investigated under a surrounding wood fire. Due to a higher heat flux to the substance, the mass burning rate reaches multiples of an equivalent pool fire and results in several fireballs. The analyses of thermographic camera images and radiometer measurements show higher flame lengths, higher temperatures and therefore increased thermal radiation compared to OP pool fires. The resulting greater safety distances for a DTBP fireball event are discussed. T2 - New Trends in Research of Energetic Materials (NTREM) CY - Pardubice, Poland DA - 20.04.2016 KW - Organic peroxide KW - Pool fire KW - Fireball KW - Thermal radiation KW - Safety distance PY - 2016 AN - OPUS4-36009 LA - eng 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 JF - Chemical engineering and processing 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 DO - 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 - Fritzsche, Lutz A1 - Knorr, Annett T1 - Continuous synthesis of a high energetic substance using small scale reactors T2 - ICheaP11 - 11th International conference on chemical & process engineering (Proceedings) 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 DO - 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 - CHAP A1 - Schönbucher, A. A1 - Schälike, Stefan A1 - Vela-Wallenschus, Iris A1 - Wehrstedt, Klaus-Dieter ED - Schmidt, J. T1 - CFD simulation of large hydrocarbon and peroxide pool fires T2 - Process and plant safety: applying computational fluid dynamics KW - Pool fire KW - JP 4 KW - Organic peroxide KW - DTBP KW - CFD KW - Surface emissive power KW - Irradiation KW - Safety distances PY - 2012 SN - 978-3-527-33027-0 N1 - Geburtsname von Vela-Wallenschus, Iris: Vela, I. - Birth name of Vela-Wallenschus, Iris: Vela, I. IS - Chapter 9 SP - 139 EP - 157 PB - Wiley-VCH Verlag GmbH & Co. KGaA AN - OPUS4-25897 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mishra, Kirti Bhushan A1 - Wehrstedt, Klaus-Dieter T1 - Combustion of peroxy-fuels T2 - ERCOFTAC conference - Highly resolved experimental and numerical diagnostics for turbulent combustion -HRTC-1- (Proceedings) N2 - The diffusion flames of organic peroxides exhibit quite different characteristics than hydrocarbons. What makes them interesting to study is their fast burning behaviour. As a result the flame temperature enhances and so does the thermal radiation. Due to all these they demand safe handling during processing. However, they can be utilised at several places in different industries where a fuel with fast burning, high temperature and intense radiation are desired. Some of the possibilities to use them as a main or supporting fuel in a wide range of industrial utilities are the major content of this paper. T2 - ERCOFTAC conference - Highly resolved experimental and numerical diagnostics for turbulent combustion CY - Rouen, France DA - 25.05.2011 KW - Energetic materials KW - Process industries KW - Organic peroxide KW - Di-tert-butyl peroxide (DTBP) KW - CFD simulation KW - Emission PY - 2011 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-247083 SP - 1 EP - 5 AN - OPUS4-24708 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mishra, Kirti Bhushan A1 - Wehrstedt, Klaus-Dieter T1 - An efficient and clean fuel for high temperature process industries T2 - 11th Conference on energy for a clean environment N2 - The use of energetic materials as a main fuel in high temperature process industries are not known to the scientific community as such. This paper highlights some of the features and advantages of using organic peroxides especially di-tert-butyl peroxide (DTBP) in high temperature process industries. The feasibility of using DTBP as a main or supporting fuel in process industries have also been justified with the help of Computational Fluid Dynamics (CFD) simulations. For peroxides requirement of less fuel and air for the same amount of heat flux has been shown. The resulted emission from the combustion of DTBP is also discussed. T2 - 11th Conference on Energy for a Clean Environment CY - Lisbon, Portugal DA - 2011-07-05 KW - Energetic materials KW - Process industries KW - Organic peroxide KW - Di-tert-butylperoxide (DTBP) KW - CFD simulation KW - Emission PY - 2011 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-247071 SP - 1 EP - 10 AN - OPUS4-24707 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mishra, Kirti Bhushan A1 - Wehrstedt, Klaus-Dieter T1 - Burner for peroxy-fuels (PEROXY-BAM Burner) T2 - VDI-Berichte - 25. Deutscher Flammentag - Verbrennung und Feuerung N2 - A new burner concept (PEROXY-BAM®) for the combustion of liquid organic peroxides (Peroxy-fuels) is presented. As peroxy-fuels are thermally unstable the design of burners for them should be accordingly modified ensuring a safe operation. It is found that 10 to 100 time less amounts of peroxy fuels are required for the same heat flux or output in comparison to hydrocarbons. Correspondingly, the fuel pump power and the volume of combustion chamber (furnace) are also reduced. As a result of less amount of fuel the emissions will also be stepped down and oxygen in the molecule helps to establish conditons like in an oxy-fuel combustion process. The advantages of using peroxy-fuels over hydrocarbons inside a model combustion chamber are also investigated with the help of CFD (Computational Fluid Dynamics) simulations. T2 - 25. Deutscher Flammentag - Verbrennung und Feuerung CY - Karlsruhe, Germany DA - 14.09.2011 KW - Organic peroxide KW - Peroxy-fuel KW - Burner concept KW - Combustion KW - Combustion chamber PY - 2011 SN - 978-3-18-092119-8 SN - 0083-5560 N1 - Serientitel: VDI-Berichte – Series title: VDI-Berichte VL - 2119 SP - 307 EP - 312 PB - VDI-Verl. AN - OPUS4-24388 LA - eng 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 JF - Journal of hazardous materials 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 DO - 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 -