EP0932432B1 - Labiles brom enthaltende feuerlöschsubstanz - Google Patents

Labiles brom enthaltende feuerlöschsubstanz Download PDF

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Publication number
EP0932432B1
EP0932432B1 EP96936260A EP96936260A EP0932432B1 EP 0932432 B1 EP0932432 B1 EP 0932432B1 EP 96936260 A EP96936260 A EP 96936260A EP 96936260 A EP96936260 A EP 96936260A EP 0932432 B1 EP0932432 B1 EP 0932432B1
Authority
EP
European Patent Office
Prior art keywords
brf
fire
pbr
liquid
bromine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96936260A
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English (en)
French (fr)
Other versions
EP0932432A1 (de
Inventor
Peter D. Haaland
John H. Huntington
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eclipse Aerospace Inc
Original Assignee
PHYRX Ltd
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Publication date
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Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007—Solid extinguishing substances
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0092—Gaseous extinguishing substances, e.g. liquefied gases, carbon dioxide snow

Definitions

  • the present invention generally relates to prevention and extinguishment of fires of combustible materials by utilizing a composition of matter group which is highly efficient and environmentally friendly. More particularly, the invention relates to prevention and extinguishment of fires of combustible materials by using a group of fire suppressants having labile bonds between bromine atoms and atoms other than carbon.
  • Fire suppression by halogenated alkanes is well-established in both the scientific literature and commercial practice as taught, for example, in R.G. Gann ed., Halogenated Fire Suppressants, ACS Symposium Series 16 (American Chemical Society, Washington, D.C.) 1975.
  • the two most widely used halogenated suppressants are Halon 1301 (CF 3 Br) and Halon 1211 (CF 2 ClBr). These compounds are very stable, so they survive long enough in the troposphere to be gradually transported to the stratosphere, where they are photolyzed by solar ultraviolet radiation to produce free radicals that catalyze ozone depletion as taught, for example, in J.G. Anderson, D.W. Toohey, and W.F. Brune, Science, 251, 39 (1991).
  • a fire suppressant composition consisting essentially of at least one compound with bromine bound to atoms other than carbon selected from the group consisting of PBr 3 , POBr 3 , SOBr 2 , BrF 3 , BrF 5 , PBr 5 , TiBr 4 , SiBr 4 , IBr, CuBr, NOBr, BrF, BBr 3 , C 4 H 4 O 2 NBr, and BrCI combined with a propellant wherein the ozone depletion potential of the composition is less than 0.1.
  • the ozone depletion potential of such a fire suppressant composition is defined on a scale where the ozone depletion caused by CFCl 3 is 1.0.
  • a fire suppressant composition consisting of at least one labile brominating compound selected from the group consisting of PBr 3 , POBr 3 , SOBr 2 , BrF 3 , BrF 5 , TiBr 4 , SiBr 4 , IBr, CuBr, NOBr, BrF, BBr 3 , and BrCI combined with a propellant selected from the group consisting of CO 2 , N 2 , compressed air, and HCFC-123 (CF 3 CCl 2 H).
  • the ozone depletion potential of the propellant of this embodiment equals 0.016.
  • compositions of matter having labile bromine atoms bound to atoms other than carbon have been discovered to have improved fire suppressant properties and to be environmentally friendly.
  • Compounds which release bromine atoms and are commonly used as brominating agents in organic synthesis such as phosphorous tribromide (PBr 3 ), thionyl bromide (SOBr 2 ), boron tribromide (BBr 3 ), and the like are very efficient at extinguishing fires. Moreover, they hydrolyze or oxidize rapidly in the troposphere and consequently they have no stratospheric ozone depletion potential.
  • SiBr 4 silicon tetrabromide
  • TiBr 4 titanium tetrabromide
  • IBr iodine bromide
  • POBr 3 phosphorous oxybromide
  • BrF 3 bromine trifluoride
  • bromine pentaflouride (BrF 5 ) N-bromosuccinimide (C 4 H 4 O 2 NBr) ⁇ the bromine is bound to nitrogen, not carbon ⁇ , nitrosyl bromide (NOBr) chlorine bromide (ClBr), and cuprous bromide (CuBr).
  • non-labile bromine compositions are found in such high-melting, ionically bound salts as lithium bromide (LiBr, m.p. 547° C), calcium bromide (CaBr 2 , m.p. 730° C), or chromous bromide (CrBr 2 , m.p. 842° C), and other bromine-containing compositions that are thermally and oxidatively stable according to criteria familiar to people practiced in the art of synthetic chemistry.
  • lithium bromide LiBr, m.p. 547° C
  • CaBr 2 calcium bromide
  • CrBr 2 chromous bromide
  • equipment for delivering the composition incorporates such factors as specific geometry, gas flow, and flame conditions.
  • a method of delivery of a composition having one or more liquid compounds of the aforesaid class of fires suppressants may employ a nonflammable, pressurized gas to propel the composition through a nozzle to the flame.
  • Another method of delivery of liquid compositions may employ a deflagrating solid, gas-generating cartridge, such as is found in automotive airbags, to propel a mist of liquid to the flame.
  • a third method for delivery of liquid compositions may employ a pressurized liquid propellant such as liquid carbon dioxide or liquid argon to atomize and direct a mist of suppressant onto the flame.
  • a pressurized liquid propellant such as liquid carbon dioxide or liquid argon
  • Other methods for propelling powders or slurries of solid materials of the aforesaid class may employ a deflagrating solid gas generating cartridge and a wider nozzle such as would be used for an ordinary shotgun cartridge.
  • Other methods for propelling gaseous materials of the aforesaid class may employ mixtures with pressurized inert propellants to aid transport of suppressant to the flame.
  • the primary advantage of the use of the class of fire suppressants of this discovery is to extinguish fires more efficiently with smaller volumes without depleting the stratospheric ozone layer.
  • PBr 3 , POBr 3 , SOBr 2 , BBr 3 , and the like react rapidly with water vapor or liquid to produce mild acids which precipitate with normal rain and are ultimately neutralized in soils.
  • the short lifetimes of these materials also reduce toxicity of the suppressants since their simple acid decomposition products pose no chronic risk to pH buffered, living organisms.
  • the effectiveness of the class of suppressants described herein is a result of the relative ease with which bromine atoms are liberated in a flame environment.
  • Halons 1301 and 1211 also liberate bromine atoms in a flame; however, the strength of the C-Br bond in these materials requires higher temperatures or longer interaction times than the compositions of matter described herein.
  • the stability of the Halons against oxidation or hydrolysis in the troposphere is one indication of the stability of the C-Br bond.
  • the compositions of matter described herein are not stable in the presence of water, oxygen, or heat, liberating bromine atoms under these conditions and thereby providing a catalyst for flame suppression.
  • Another indication of the stability of the C-Br bond is the measurement of its bond dissociation energy of 68 kilocalories per mole as taught by A.H. Sehon and M. Szwarc (Proceedings of the Royal Society (London), page 110, [1951]). This energy is larger than the bond energy of typical P-Br bonds (63 kcal/mole), I-Br bonds (43 kcal/mole), or S-Br bonds (52 kcal/mole) as taught by Streitweiser and Heathcock, Introduction to Organic Chemistry, (Macmillian:NY), 1976 and Cotton and Wilkinson, Advanced Inorganic Chemistry, (3rd ed. Wiley:NY), 1972.
  • liquid SOBr 2 is introduced as an air-pressurized mist into a 500,000 Btu/hr fire resulting from kerosene flowing at a rate of 4 grams per second through a nozzle with cross-flowing compressed air to atomize the liquid into a fine mist.
  • the fire is contained in a flame holder whose volume is approximately 8 liters and is further blown by an atmospheric cross-wind of 64 km per hour (40 miles per hour).
  • the fire is reproducibly and irreversibly extinguished with less than one gram of SOBr 2 in less than 0.2 seconds as confirmed by videotape records of the experiments.
  • the same fire is not reproducibly suppressed with aliquots of 25 grams of CF 3 Br added to the same location.
  • PBr 3 0.2 cubic centimeters of PBr 3 is mixed with 0.7 cubic centimeters of liquid carbon dioxide.
  • the liquid CO 2 propels the PBr 3 through a valve and into the flame zone, generated as herein above described, as it is opened, irreversibly and completely extinguishing the flame in the presence of flowing fuel, air, and hot surfaces.
  • Halon 1301 Extinguishment of a similar fire, with a hydrocarbon fuel burn rate of 12 grams per second, by Halon 1301 is taught by Alvarez in chapter 3 of Gann (ibid.) to require between 90 and 130 grams per second of CF 3 Br for suppression.
  • Another example of a gasoline fire with similar heat output is taught by Ford in chapter 1 of Gann (ibid.) to require between 500 and 1500 grams of Halon 1301 for suppression.
  • Another fire, in which 10 grams per second of jet fuel are burned in fast-flowing air at the Air Force Flight Dynamics Laboratory Engine Nacelle test facility (Wright-Patterson AFB, OH) requires between one and three kilograms of Halon 1301 for reproducible suppression.
  • the quantity of Halon 1301 required to suppress a similar fire is between 100 and 1000 times greater than that required of the compositions of matter described herein above, of which SOBr 2 and PBr 3 are specific embodiments.
  • the labile bromine atoms and high proportion of bromine in the composition of matter listed in Table I provide a more efficient fire suppression formulation than the Halons, which typically have less bromine by weight (Halon 1301 and 1211 are 54% and 48% Br, respectively) and lesser proclivity for liberating bromine atoms when thermally or chemically activated in a combustion environment.
  • Methods for dispersing gas, liquid, or solid suppressants require designs based upon such factors as specific geometry of the locus of the fire, flow properties of the fire suppressants, and flame conditions of the fire. For example, fine mists of liquid are transported by fluid-dynamical drag forces along flow streamlines in the nacelle of an aircraft engine. The mists vaporize in hot zones, liberating bromine atoms by pyrolysis in precisely the regions where the heat released by combustion is most intense. Inasmuch as the drag coefficient is inversely proportional to the droplet diameter, as is known to people practiced in the art of fluid dynamics, there is a range of aerosol size distributions which most effectively deliver specific suppressants to specific fires.
  • Dispersing methods designed for suppressing fire in the nacelle of a jet engine differ from dispersing methods designed for suppressing fire in the engine compartment of a motor vehicle, the flu of a chimney, or the gas-handling manifold of a semiconductor processing clean-room.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Fireproofing Substances (AREA)

Claims (3)

  1. Zusammensetzung für eine Feuerlöschsubstanz, im wesentlichen enthaltend zumindest eine Verbindung die Brom gebunden an ein anderes Atom als Kohlenstoff enthält, ausgewählt aus der Gruppe, die gebildet wird von PBr3, POBr3, SOBr2, BrF3, BrF5, PBr5, TiBr4, SiBr4, IBr, CuBr, NOBr, BrF, BBr3, C4H4O2NBr und BrCl, in Kombination mit einem Treibmittel, wobei das Potential der Zusammensetzung zur Vernichtung von Ozon weniger als 0,1 beträgt, wobei das Vernichtungspotential für Ozon auf einer Skala definiert ist, auf der die Ozonvernichtung durch CFCl3 als 1,0 definiert ist.
  2. Zusammensetzung für eine Feuerlöschsubstanz enthaltend zumindest eine labile Bromierungsverbindung ausgewählt aus der Gruppe, die gebildet wird von PBr3, POBr3, SOBr2, BrF3, BrF5, TiBr4, SiBr4, IBr, CuBr, NOBr, BrF, BBr3, und BrCl in Kombination mit einem Treibmittel ausgewählt aus der Gruppe, die gebildet wird von CO2, N2, komprimierter Luft und HCFC-123 (CF3CCl2H).
  3. Zusammensetzung für eine Feuerlöschsubstanz nach Anspruch 2, wobei das Ozonvernichtungspotential des Treibmittels 0,016 beträgt.
EP96936260A 1996-10-08 1996-10-08 Labiles brom enthaltende feuerlöschsubstanz Expired - Lifetime EP0932432B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/016089 WO1998015322A1 (en) 1996-10-08 1996-10-08 Labile bromine fire suppressants

Publications (2)

Publication Number Publication Date
EP0932432A1 EP0932432A1 (de) 1999-08-04
EP0932432B1 true EP0932432B1 (de) 2000-05-31

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EP (1) EP0932432B1 (de)
JP (1) JP3868500B2 (de)
AU (1) AU7395296A (de)
DE (1) DE69608707T2 (de)
WO (1) WO1998015322A1 (de)

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* Cited by examiner, † Cited by third party
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KR101514177B1 (ko) 2005-01-12 2015-04-22 이클립스 에어로스페이스, 인크. 화재 진압 시스템

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* Cited by examiner, † Cited by third party
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SU981338A1 (ru) * 1981-06-29 1982-12-15 Всесоюзный научно-исследовательский институт противопожарной обороны МВД СССР Ингибитор горени
SU1673141A1 (ru) * 1989-03-23 1991-08-30 Стахановский Филиал Коммунарского Горно-Металлургического Института Способ получени состава дл тушени пожаров

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Publication number Publication date
DE69608707T2 (de) 2000-11-23
WO1998015322A1 (en) 1998-04-16
DE69608707D1 (de) 2000-07-06
AU7395296A (en) 1998-05-05
EP0932432A1 (de) 1999-08-04
JP3868500B2 (ja) 2007-01-17
JP2001501523A (ja) 2001-02-06

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