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Tetrafluoroethylene (TFE) is an industrial scale starting material e.g. for polymer production (PTFE, FEP). When ignited the chemically unstable TFE is capable of decomposing in an explosive way. Explosion propagation through pipe systems of production plants have led to damage and fatalities within the last seven decades.
Incident analyses identified compression heat a relevant source of ignition. Chemical plants consist of pipes, vessels, separating valves, strainers and other components. Before restarting the process after maintenance work, different parts of the plant components could be filled with TFE, nitrogen or air at different initial pressures ranging from vacuum or atmospheric to TFE at operating pressure. Valve opening procedures may cause a temperature increase in the gas phase. Compression takes place at polytropic conditions. Heat losses cannot be neglected. The temperature development in the gas depends upon the surface to volume ratio of the enclosure, geometrical influences, the state of gas flow, how fast the valve opens, and the heat capacity of the gas being compressed.
Laboratory scale tests (Meyer, 2009) revealed ignition of TFE/air due to compression heat. Tests in pipes of 28 mm inner diameter, i.e. already industrial scale, were performed by (Kluge et. al., 2016). In the present contribution initial test results from a 63 mm pipe will be compared with existing 28 mm pipe data. A description of the experimental setup as well as an explanation of the hazard diagram will be given.
Furthermore, a method allowing for the identification of hazardous conditions will be discussed.
The selective gas phase oxidation of o-xylene was investigated inside of the explosion regime using a microstructured reactor. The V2O5/TiO2 catalyst was used as microfixed bed and as catalyst coating. There were no significant losses of the selectivity to phthalic anhydride with feed compositions up to 7 vol % o-xylene observable. Above 7 vol % the selectivity decreased due to total oxidation, especially for the microfixed bed, which was probably caused by a hotspot.
Investigations on primary, secondary and tertiary explosion protection have been performed for micro reactors with slit-like channels which are coated with catalyst. Ethene/oxygen mixtures have been used as model gas mixtures representing explosion group IIB (DIN EN ISO 16852). It could be shown that the explosion regime can be significantly reduced when using micro reactors (primary explosion protection). Furthermore, safe Operation inside the explosion regime is possible with micro reactors (secondary explosion protection), but, at certain conditions thermal runaway and ignition of detonations are possible. An unexpected behaviour has been found, because thermal runaway occurred when Volumetrie flow rate was increased. This behaviour is completely opposite to that of multi tube fixed bed reactors which show an increase of safety when increasing volumetric flow rate. Micro reactors can be constructed pressure-resistant even when detonations occur inside (tertiary explosion protection). For the example of o-xylene oxidation it could be shown that space time yield can be increased significantly when entering explosion regime.
Sicherheit µ-strukturierter Apparate: Untersuchungsmethoden zur Explosionsausbreitung (Gasphase)
(2010)
Are micro reactors inherently safe? - An investigation of gas phase explosion propagation limits
(2010)
Die Mikroverfahrenstechnik beschäftigt sich mit Apparaten, deren innere Abmessungen kleiner als ein Millimeter sind. Mikroreaktoren sind zurzeit Gegenstand intensiver Forschungsarbeit. Aus Sicht der chemischen Sicherheitstechnik besteht eines von mehreren Zielen bei der Entwicklung von Mikroreaktoren darin, schwer beherrschbare Reaktionen bei Reaktionsbedingungen zu realisieren, die in konventionellen Chemieanlagen wegen ihrer besonderen Gefährlichkeit nicht mehr beherrscht werden können. Der große spezifische Wärmeaustausch kann das thermische Durchgehen der Reaktion verhindern, die engen Abmessungen können die Ausbreitung von Explosionen unterdrücken. Bei mehrstufigen Synthesen kann die Lagerung giftiger oder zersetzungsfähiger Zwischenprodukte durch unverzügliche weitere Umsetzung in einem folgenden Reaktionsschritt vermieden werden. Der vorliegende Beitrag widmet sich sicherheitstechnischen Aspekten der Mikroverfahrenstechnik.
The polymeric industry handles Tetrafluoroethylene (TFE) as basic material for polymer (PTFE) and co-polymer (PCTFE) production. As a chemically unstable gas, it can react in an explosive way, without the presence of any other gases. Once initiated such an exothermic reaction can propagate through the pipe system of a plant and might lead to massive damages and/or fatalities. Especially after maintenance parts of the pipe systems can be filled with TFE, nitrogen or air at pressures up to atmospheric conditions whereas connected parts of pipes might still contain TFE at operating pressure state. Many of the regarding pipes are separated by ball valves, which allow a fast opening procedure. Thereby fast compression of the gas can occur and lead to a massive temperature increase which might induce unwanted reactions. Former tests in laboratory scale described by Meyer (2009) allowed an ignition of a TFE/air system by rapid compression only for a set of sharp defined boundary conditions. First tests in the lower industrial scale were done by Ferrero et al. (2013), where an ignition at typical industrial operating conditions was initiated. The results of the tests indicated that the critical achievable compression temperatures strongly depend on the setup and therefore on the pipe diameter as well. Therefore the necessity of further tests has been pointed out. The original setup presented by Ferrero (2013), which represents the smallest typical industrial size with an inner diameter of 1.125”, was modified to withstand an explosive decomposition reaction and to avoid a deflagration to detonation transition. Different safety concepts as burst discs and time controlled cut-off valves had been tested and evaluated to optimize the experimental setup for reproducible test conditions. This allowed the systematic investigation of the rapid compression of TFE–systems for the first time in the described scale without serious damages after an ignition. In the donor pipe always TFE at high pressure and in the receiving pipe TFE, nitrogen or air were present at an absolute pressure ranging from 500 Pa to atmospheric pressure.
The scope was to generate a “hazard diagram” in which the ignition probability in dependence of donor (high) pressure and the receiving (low) pressure is shown. Hazardous conditions can easily be determined. A reference method for the maximum achievable temperatures of non-reacting gas systems was created using an air/air-system. Thus reactive TFE-systems could be evaluated regarding additional exothermic effects. The final hazard diagram demonstrates that there is no sharp limit between a “safe” state and an “ignition” for a TFE/air-system. Rather a transition range exists, which decreases with rising donor pressure. An increased temperature in this range, sometimes combined with small pressure peaks in the profile, indicates first partial restricted reactions near the end flange. The more it gets closer to the “ignition” transition the more traces like soot or undefined solid fractions were found. A TFE/nitrogen- and a TFE/TFE-system could not be ignited at all. A description of the experimental tests as well as a detailed explanation of the hazard diagram will be presented.
Tetrafluorethen wird von der Polymerindustrie seit Jahrzenten als monomeres Ausgangsmaterial sowohl für die Herstellung von Polymeren (PTFE) als auch für Kopolymere (PCTFE) eingesetzt. Aufgrund seiner Eigenschaft als chemisch instabiles Gas kann TFE auch ohne Luftsauerstoff oder einen anderen Oxydator explosionsartig zerfallen. Nach der Initiierung des Zerfalls kann dieser unter bestimmten Bedingungen aufgrund des exothermen Reaktionsverhaltens sich selbstständig in Apparaten und Rohrleitungen ausbreiten. Dies geht aufgrund der freigesetzten Reaktionsenthalpie mit einem schlagartigen Anstieg von Druck und Temperatur einher, was zu erheblichen Belastungen der Materialien bis hin zum Versagen und Bruch und möglichen Folgeschäden einschließlich Personenschäden führen kann und in der Vergangenheit bereits mehrfach geführt hat.
Besonders nach Wartungsarbeiten besteht die Gefahr, dass Teilabschnitte im Rohrleitungssystem mit TFE, Stickstoff oder Luft gefüllt sind mit Drücken in einem Bereich zwischen technischem Vakuum und atmosphärischem Druck wohingegen angrenzende Rohrabschnitte oder Behälter immer noch TFE bei Betriebsdrücken bis 32 bar enthalten können. Dabei sind die Abschnitte in der Praxis häufig durch Kugelhähne voneinander getrennt, die aufgrund ihrer Öffnungscharakteristik bereits bei geringen Betätigungswinkeln eine große Querschnittsfreigabe für die Strömung im Rohr ermöglichen. Dadurch können schlagartige Kompressionsvorgänge des Gases im Niederdruckbereich ermöglicht werden, die allein aufgrund der thermodynamischen Zustandsänderung zu einer erheblichen Temperaturerhöhung führen und im schlimmsten Fall zur Initiierung der Zerfallsreaktion führen können.
Es wird erstmalig ein Versuchsaufbau im Industriemaßstab, der einer explosionsartigen Zerfallsreaktion von TFE standhalten kann. Zahlreiche Sicherheitskonzepte einschließlich diverser Berstscheibenkonfigurationen als auch zeitgesteuerte Schnellschlussventile wurden eingehend untersucht und bewertet, um die optimale Versuchskonfiguration für bestmögliche Reproduzierbarkeit festzulegen. Es fand eine systematische Untersuchung der schlagartigen Kompression der Systeme Luft/Luft, TFE/Luft, TFE/TFE und TFE/N2 statt. In der Hochdrucksektion wurden Drücke bis 30 bar realisiert und im Niederdrucksektor konnten Anfangsdrücke im Bereich weniger Millibar bis hin zu Atmosphärendruck eingestellt werden. Als Hauptergebnis wurde ein „Hazard diagram" erstellt, mit dessen Hilfe die Zündwahrscheinlichkeit in Abhängigkeit vom Hochdruck und Niederdruck abgeschätzt werden kann. Gefährliche Bedingungen in Rohrleitungen können dadurch auf einfachem Weg identifiziert werden. Als Referenzsystem zur Beurteilung der maximal erreichbaren nicht reaktiven Kompressionstemperaturen wurde Luft/Luft verwendet. Die damit ermittelten Daten dienten zur Bewertung von zusätzlichen exothermen Effekten, wie sie etwa bei Vorreaktion des TFE im Falle einer Dimerisierung auftreten können.
Entgegen der ursprünglichen Annahme konnten die Systeme TFE/Stickstoff und TFE/TFE im verwendeten Aufbau nicht durch Kompressionsvorgänge gezündet werden.
Explosion protection of oxidation reactions in micro reactors was investigated. Lange et al. (2014) reported on the possibilities of operating oxidation reactions in catalyst coated micro reactors within the explosion regime, but also warned about hotspot induced thermal runaway and detonation ignition at certain conditions. Methane and ethene, representing the explosion groups IIA1 and IIB (DIN EN ISO 16852), were used in stoichiometric oxygen mixtures with respect to total oxidation, which represents the worst case scenario in terms of safety assessment. Using laser radiation on a ceramic target inside of the micro channel, an artificial, controllable hotspot was generated. The ignition temperatures of fuel gas/oxygen mixtures inside a micro reactor were measured and their dependencies on initial pressure, initial temperature, volumetric flow rate, and micro channel height were examined. Deflagration reactions prior to the detonation were observed for the first time inside a micro reactor.
For a comprehensive safety assessment of stationary lithium-ion-battery applications, it is necessary to better understand the consequences of thermal runaway (TR). In this study, experimental tests comprising twelve TR experiments including four single-cell tests, two cell stack tests and six second-life module tests (2.65 kW h and 6.85 kW h) with an NMC-cathode under similar initial conditions were conducted. The temperature (direct at cells/modules and in near field), mass loss, cell/module voltage, and qualitative vent gas composition (Fourier transform infrared (FTIR) and diode laser spectroscopy (DLS) for HF) were measured. The results of the tests showed that the battery TR is accompanied by severe and in some cases violent chemical reactions. In most cases, TR was not accompanied by pregassing of the modules. Jet flames up to a length of 5 m and fragment throwing to distances to more than 30 m were detected. The TR of the tested modules was accompanied by significant mass loss of up to 82%. The maximum HF concentration measured was 76 ppm, whereby the measured HF concentrations in the module tests were not necessarily higher than that in the cell stack tests.
Subsequently, an explosion of the released vent gas occurred in one of the tests, resulting in the intensification of the negative consequences. According to the evaluation of the gas measurements with regard to toxicity base on the “Acute Exposure Guideline Levels” (AEGL), there is some concern with regards to CO, which may be equally as important to consider as the release of HF.
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Tetrafluoroethylene (TFE) is an industrial scale starting material e.g. for polymer production (PTFE, FEP). When ignited the chemically unstable TFE is capable to decompose in an explosive way. Explosion propagation through pipe systems of production plants have led to damage and fatalities within the last 7 decades.
Incident analyses identified compression heat a relevant source of ignition. Chemical plants consist of pipes, vessels, separating valves, strainers and other components. Before restarting the process after maintenance work different parts of the plant components could be filled with TFE, Nitrogen or Air at different initial pressures ranging from vacuum or atmospheric to TFE at operating pressure. Valve opening procedures may cause a temperature increase in the gas phase. Compression takes place at polytropic conditions. Heat losses cannot be neglected. Therefore the temperature development in the gas depends upon the surface-to-volume-ratio of the enclosure, geometrical influences, the state of gas flow, how fast the valve opens and the heat capacity of the gas being compressed.
In the present work initial test results from a 2.5” pipe will be compared with existing 1.1” pipe data. Geometrical effects will be briefly discussed as well as some first results concerning the influence of orifices are reported. Furthermore a method allowing for the identification of hazardous initial conditions is discussed.