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Hydrogen Fluoride) Production from Halon 1301 and Alternative Gaseous Fire Suppressants a Review

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Hydrogen Fluoride) Production from Halon 1301 and Alternative Gaseous Fire Suppressants a Review Acid gas (hydrogen fluoride) production from Halon 1301 and alternative gaseous fire suppressants A Review John A. Hiltz DRDC – Atlantic Research Centre Defence Research and Development Canada Scientific Report DRDC-RDDC-2015-R036 March 2015 IMPORTANT INFORMATIVE STATEMENTS This work was carried out as part of the Naval Platforms Project – 01 ea. © Her Majesty the Queen in Right of Canada, as represented by the Minister of National Defence, 2015 © Sa Majesté la Reine (en droit du Canada), telle que représentée par le ministre de la Défense nationale, 2015 Abstract …….. Halon 1301 (CF3Br) is used as a total flooding fire suppression gas on Royal Canadian Navy ships and submarines. Because it is an ozone depleting substance it will not be used on new build naval vessels. There are a number of non-ozone depleting gaseous agents that have been evaluated as alternatives for Halon 1301 for use in normally occupied spaces. These include FE-13 (HFC-23 or CHF3), NAF-S111 (HCFC Blend), FM-200 (HFC-227ea or CF3CHFCF3, PFC-410 or CEA 410 (C4F10), and Novec 1230 (1,1,1,2,2,4,5,5,5-nonafluoro-4-trifluoromethylpentan-3-one). A concern associated with all these gaseous agents is the release of acid gases such as hydrogen fluoride (HF) when they are exposed to high temperatures and hot surfaces. The concentrations of an acid gas such as HF will have a direct impact on the risks to firefighters during re-entry procedures. In this report the results of research on the factors affecting the concentration of HF in a space after discharge of Halon 1301 or alternative gaseous agents are reviewed. The results indicate that Halon 1301 produces significantly less HF than the alternative agents. HF production from any of the agents is very dependent on the rate at which it is introduced into the space and its design concentration. The use of ventilation and water spray or water mist to reduce the airborne concentration of HF in a space after a fire have also been studied and the results of evaluations are also included. Significance to defence and security Fire suppressant gases used on both current and future Royal Canadian Navy (RCN) vessels have or may have the potential to produce hazardous thermal degradation products such as HF. An understanding of severity of the risks associated with gaseous agent and how these can be reduced can be used to reduce hazards associated with their use on RCN vessels. In particular this information can be used to modify standards procedures for, for instance, the re-entry into a space where a gaseous agent has been discharged. The research reviewed in this report indicates that both ventilation of a space and the use of water spray or water mist before, during or after discharge of the gaseous agent will reduce airborne concentrations of acid gases substantially. DRDC-RDDC-2015-R036 i Résumé …….. L’halon 1301 (CF3Br) est utilisé comme gaz d’extinction d’incendie par noyage total sur les navires et les sous-marins de la Marine royale canadienne (MRC). Ce produit ne sera toutefois pas employé à ces fins sur les nouveaux navires militaires, car il constitue une substance appauvrissant la couche d’ozone. Il existe un certain nombre d’agents chimiques gazeux n’appauvrissant pas la couche d’ozone qui ont été évalués comme produits de remplacement de l’halon 1301 dans les endroits normalement occupés. Ces produits comprennent le FE-13 (HFC-23 ou CHF3), le NAF-S111 (un mélange de HCFC), le FM-200 (HFC-227ea ou CF3CHFCF3), le PFC-410 ou CEA 410 (C4F10), et le Novec 1230 (1,1,1,2,2,4,5,5,5-nonafluoro-4-trifluorométhylpentan-3-one). L’utilisation de tous ces agents chimiques gazeux suscite toutefois quelques inquiétudes, particulièrement l’émission de gaz acides comme le fluorure d’hydrogène (HF), lorsque les agents chimiques en question sont exposés à des températures élevées et des surfaces chaudes. La concentration d’un gaz acide comme le HF a une incidence directe sur les risques que courent les pompiers lorsqu’ils doivent retourner dans le foyer d’incendie. Le présent rapport comporte un examen des résultats de travaux de recherche portant sur les facteurs qui influent sur la concentration de HF là où s’est produite une émission d’halon 1301 ou d’agents chimiques gazeux de remplacement. Les résultats indiquent que l’halon 1301 produit beaucoup moins de HF que les agents chimiques de remplacement. La production de HF par ces derniers dépend grandement de la vitesse à laquelle il pénètre dans l’endroit étudié et de sa concentration nominale. L’étude porte aussi sur l’utilisation d’appareils de ventilation et d’extincteurs à eau pulvérisée ou à brouillard d’eau pour réduire la concentration de HF en suspension dans l’air ambiant en un endroit donné, à la suite d’un incendie. Le présent rapport comporte aussi les résultats des évaluations. Importance pour la défense et la sécurité Les gaz d’extinction d’incendie utilisés sur les navires actuels de la Marine royale canadienne (MRC), ou qui le seront sur de futurs navires militaires, peuvent ou pourraient dégager des produits de dégradation thermique dangereux comme le HF. La compréhension de la gravité des risques associés aux agents chimiques gazeux et des mesures permettant de réduire ces risques sera d’une grande utilité, car les résultats serviront à réduire les risques relatifs à l’emploi de ces substances sur les navires militaires de la MRC. Les renseignements colligés pourront notamment être utilisés pour modifier les procédures normalisées ayant trait, par exemple, au fait de retourner dans un endroit où un agent chimique gazeux a été libéré. Les résultats de recherche examinés dans le présent rapport indiquent que la ventilation d’un endroit donné et l’utilisation d’extincteurs à eau pulvérisée ou à brouillard d’eau, et ce, avant, pendant ou après la libération de l’agent chimique gazeux, permettent, dans tous les cas, de réduire grandement la concentration de gaz acides en suspension dans l’air ambiant. ii DRDC-RDDC-2015-R036 Table of contents Abstract …….. ................................................................................................................................. i Significance to defence and security ................................................................................................ i Résumé …….. ................................................................................................................................. ii Importance pour la défense et la sécurité ........................................................................................ ii Table of contents ............................................................................................................................ iii List of figures ................................................................................................................................. iv List of tables .................................................................................................................................... v 1 Introduction ............................................................................................................................... 1 2 Results and discussion .............................................................................................................. 2 2.1 Intermediate-scale (645 ft3) fire suppression evaluation of NFPA 2001 agents [1] ........ 2 2.2 Intermediate scale Halon 1301 replacement total flooding fire testing [2] ..................... 5 2.3 Large scale (840 m3) Hydrofluorocarbon (HFC) total flooding fire extinguishment testing [3] ......................................................................................................................... 8 2.4 Halon 1301 replacement testing—Post fire suppression compartment characterization [4] ........................................................................................................ 10 2.5 Large scale (500 m3) evaluation of gaseous agents [6] ................................................. 14 2.6 Generalized data correlations for extinguishment times and acid concentrations in fire tests with fluorinated suppression agents [9] .......................................................... 17 2.7 Thermal decomposition products of 1,1,1,2,2,4,5,5,5 nonafluoro-4-trifluoromethylpentan-3-one (Novec 1230) during small scale fire extinguishment testing [10] .............................................. 18 2.8 Novec 1230 / water mist fire suppression for machinery spaces and electronic cabinets [11] .................................................................................................................. 20 3 Conclusions and comments ..................................................................................................... 23 References ..... ............................................................................................................................... 25 DRDC-RDDC-2015-R036 iii List of figures Figure 1 HF concentration versus time for the gaseous agent fire suppression tests (from Reference [1]). ..................... 4 Figure 2 Summary of best case (minimum toxic gas production) results for the extinguishment of the 0.62 ft2 fires (from Reference [1]). ....... 4 Figure 3 Test space for the large scale (840 m3) HFC total flooding fire extinguishment testing (from Reference [3]). ............. 8 Figure 4 Concentration of HF is test space as a function of hold time (from Reference [4]). The agent (CF3CHFCF3) was released at 0 seconds. 11 Figure 5 Time versus temperature plots for the fire suppression test
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