EP0439579A1 - Methodes et melanges pour eteindre le feu, utilisant des hydrofluorocarbones. - Google Patents

Methodes et melanges pour eteindre le feu, utilisant des hydrofluorocarbones.

Info

Publication number
EP0439579A1
EP0439579A1 EP90912103A EP90912103A EP0439579A1 EP 0439579 A1 EP0439579 A1 EP 0439579A1 EP 90912103 A EP90912103 A EP 90912103A EP 90912103 A EP90912103 A EP 90912103A EP 0439579 A1 EP0439579 A1 EP 0439579A1
Authority
EP
European Patent Office
Prior art keywords
fire
halon
extinguishing
fire extinguishing
heptafluoropropane
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.)
Granted
Application number
EP90912103A
Other languages
German (de)
English (en)
Other versions
EP0439579B1 (fr
EP0439579A4 (en
Inventor
Yuichi Iikubo
Mark Lester Robin
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.)
Great Lakes Chemical Corp
Original Assignee
Great Lakes Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27015670&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0439579(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US07/439,738 external-priority patent/US5124053A/en
Application filed by Great Lakes Chemical Corp filed Critical Great Lakes Chemical Corp
Publication of EP0439579A1 publication Critical patent/EP0439579A1/fr
Publication of EP0439579A4 publication Critical patent/EP0439579A4/en
Application granted granted Critical
Publication of EP0439579B1 publication Critical patent/EP0439579B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

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
    • A62D1/0057—Polyhaloalkanes

Definitions

  • This invention relates to fire extinguishing methods and blends utilizing higher fluorinated C 2 and C 3 saturated hydrofluorocarbons.
  • hydrofluorocarbons i.e., compounds containing only C, H and F atoms
  • hydrofluorocarbons i.e., compounds containing only C, H and F atoms
  • iodine-containing compounds as fire extinguishing agents has been avoided primarily due to the expense of their manufacture or due to toxicity considerations.
  • the three fire extinguishing agents presently in common use are all bromine-containing compounds, Halon 1301 (CF 3 Br) , Halon 1211 (CF 2 BrCl) and Halon 2402 (CF 2 BrCF 2 Br) .
  • the effectiveness of these three volatile bromine-containing compounds in extinguishing fires has been described in U.S. Patent 4,014,799 to Owens.
  • certain chlorine-containing compounds are also known to be effective extinguishing agents, for example Halon 251 (CF 3 CF 2 C1) as described by Larsen in U.S. Patent 3,844,354.
  • bromine-containing Halons are effective fire fighting agents, those agents containing bromine or chlorine are asserted by some to be capable of the destruction of the earth's protective ozone layer. Also, because the agents contain no hydrogen atoms which would permit their destruction in the troposphere, the agents may also contribute to the greenhouse warming effect. It is therefore an object of this invention to provide a method for extinguishing fires that extinguishes fires as rapidly and effectively as the techniques employing presently used Halon agents while avoiding the above-named drawbacks. It is a further object of this invention to provide an agent for the use in a method of the character described that is efficient, economical to manufacture, and environmentally safe with regard to ozone depletion and greenhouse warming effects. It is a still further object of this invention to provide blends of hydrofluorocarbons and other fire extinguishing agents that are effective and environmentally safe.
  • the foregoing and other objects, advantages and features of the present invention may be achieved by employing saturated, higher fluorinated hydrofluorocarbons and blends thereof with other agents as fire extinguishants for use in fire extinguishing methods and apparatus. More particularly, the method of this invention involves introducing to a fire a saturated C 2 or C 3 higher fluorinated hydrofluorocarbon in a fire extinguishing concentration and maintaining such concentration until the fire is extinguished.
  • Saturated higher fluorinated hydrofluorocarbons of this invention include compounds of the formula C ⁇ H y F z , where x is 2 or 3; y is 1 or 2; and z is 5, 6 or 7; where y is 1 and z is 5 when x is 2 and where z is 6 or 7 when x is 3.
  • hydrofluorcarbons useful in accordance with this invention include heptafluoropropane (CF 3 CHFCF 3 ) , 1,1,1,3,3,3-hexafluoropropane (CF 3 CH 2 CF 3 ) , 1,1,1,2,3,3-hexafluoropropane (CF 3 CHFCHF 2 ) and pentafluoroethane (CF 3 CHF 2 ) .
  • CF 3 CHFCF 3 1,1,1,3,3,3-hexafluoropropane
  • CF 3 CHFCHF 2 1,1,1,2,3,3-hexafluoropropane
  • pentafluoroethane CF 3 CHF 2
  • saturated higher fluorinated C 2 and C 3 hydrofluorocarbons have been found to be effective fire extinguishants at concentrations safe for use.
  • hydrofluorocarbons contain no bromine or chlorine, they have an ozone depletion potential of zero.
  • the compounds contain hydrogen atoms, they are susceptible to breakdown in the lower atmosphere and hence do not pose a threat as greenhouse warming gasses.
  • Specific hydrofluorocarbons useful in accordance with this invention are compounds of the formula C ⁇ H y F z , where x is 2 or 3; y is 1 or 2; and z is 5, 6 or 7; where y is 1 and z is 5 when x is 2; and where z is 6 or 7 when x is 3.
  • Specific hydrofluorcarbons useful in accordance with this invention include heptafluoropropane (CF 3 CHFCF 3 ) , 1,1,1,3,3,3-hexafluoro ⁇ propane (CF 3 CH 2 CF 3 ), 1,1,1,2,3,3-hexafluoropropane (CF 3 CHFCHF 2 ) , and pentafluoroethane (CF 3 CHF 2 ) .
  • hydrofluorocarbons of this invention may be used alone or in admixture with each other or in blends with other fire extinguishing agents.
  • agents with which the hydrofluorocarbons of this invention may be blended are chlorine and/or bromine containing compounds such as Halon 1301 (CF 3 Br) , Halon 1211 (CF 2 BrCl) , Halon 2402
  • hydrofluorocarbons of this invention are employed in blends, they are desirably present at a level of at least about 10 percent by weight of the blend.
  • the hydrofluorocarbons are preferably employed at higher levels in such blends so as to minimize the adverse environmental effects of chlorine and bromine containing agents.
  • hydrofluorocarbon compounds used in accordance with this invention are non-toxic and are economical to manufacture.
  • the saturated highly fluorinated C 2 and C ⁇ hydrofluorocarbons of this invention may be effectively employed at substantially any minimum concentrations at which fire may be extinguished, the exact minimum level being dependent on the particular combustible material, the particular hydrofluorocarbon and the combustion conditions.
  • hydrofluorocarbons or mixtures and blends thereof are employed at a level of at least about 3% (v/v) .
  • hydrofluorocarbons alone best results are achieved with agent levels of at least about 5% (v/v) .
  • the maximum amount to be employed will be governed by matters of economics and potential toxicity to living things.
  • About 15% (v/v) provides a convenient maximum concentration for use of hydrofluorocarbons and mixtures and blends thereof in occupied areas. Concentrations above 15 % (v/v) may be employed in unoccupied areas, with the exact level being determined by the the particular combustible material, the hydrofluorocarbon (or mixture or blend thereof) chosen and the conditions of combustion.
  • the preferred concentration of the hydrofluorocarbon agents, mixtures and blends in accordance with this invention lies in the range of about 5 to 10% (v/v) .
  • Hydrofluorocarbons may be applied using conventional application techniques and methods used for Halons such as Halon 1301 and Halon 1211.
  • these agents may be used in a total flooding fire extinguishing system in which the agent is introduced to an enclosed region (e.g., a room or other enclosure) surrounding a fire at a concentration sufficient to extinguish the fire.
  • equipment or even rooms or enclosures may be provided with a source of agent and appropriate piping, valves, and controls so as automatically and/or manually to be introduced at appropriate concentrations in the event that fire should break out.
  • the fire extinguishant may be pressurized with nitrogen or other inert gas at up to about 600 psig at ambient conditions.
  • the hydrofluorocarbon agents may be applied to a fire through the use of conventional portable fire extinguishing equipment. It is usual to increase the pressure in portable fire extinguishers with nitrogen or other inert gasses in order to insure that the agent is completely expelled from the the extinguisher. Hydrofli -jrocarbon containing systems in accordance with this ii;mention may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions.
  • EXAMPLE 1 A 28.3 cubic litre test enclosure was constructed for static flame extinguishment tests (total flooding) .
  • the enclosure was equipped with a Plexiglas viewport and an inlet at the top for the agent to be tested and an inlet near the bottom to admit air.
  • a 90 x 50 mm glass dish was placed in the center of the enclosure and filled with 10 grams of cigarette lighter fluid available under the trademark RONSONOL.
  • the fuel was ignited and allowed a 15 second preburn before introduction of the agent. During the preburn, air was admitted to the enclosure through the lower inlet. After 15 seconds, the air inlet was closed and the fire extinguishing agent was admitted to the enclosure.
  • a predetermined amount of agent was delivered sufficient to provide 6.6% v/v concentration of the agent.
  • the extinguishment time was measured as the time between admitting the agent and extinguishment of the flame. Average extinguishment times for a 6.6% v/v concentration of heptafluoropropane, Halon 1301, Halon 1211 and CF 3 CHFBr are given in Table 1.
  • Example 2 The experimental procedure of Example 1 was carried out employing heptane as the fuel. The average extinguishment times for 6.6% v/v of the s ⁇ une agents are also given in Table 1.
  • the Table shows the extinguishment time required for various fuels at 6.6% v/v of the agents employed. At this level, heptafluoropropane is as effective as bromine-containing Halons in extinguishing an n-heptane flame and nearly effective as the other agents in extinguishing lighter fluid flames.
  • Levels of about 5-10% are preferred for general application of pure hydrofluorocarbons in accordance with this invention.
  • the use of too little agent results in failure to extinguish the fire and can result in excessive smoke and probably release of HF due to combustion of the agent.
  • the use of excessive amounts is wasteful and can lead to dilution of the oxygen level of the air to levels harmful to living things.
  • Example 1 was repeated with two white mice admitted to the chamber. After extinguishment, mice were exposed to combustion products for a total of 10 minutes before being removed from the chamber. All mice showed no ill effects during the exposure and appeared to behave normally after removal from the apparatus.
  • Halon 1211 and Halon 251 were used to extinguish n-heptane diffusion flames using the method of Example 4. Test data are reported in Table 3.
  • heptafluoropropane 1,1,1,2,3,3-hexafluoropropane and pentafluoroethane in accordance with this invention is significantly more effective than other known non-bromine or chlorine containing Halons such as Halon 14 (CF 4 ) .
  • heptafluoropropane is comparable in effectiveness to Halon 251, a chlorine containing chlorofluorocarbon. The latter relationship is shown with respect to n-heptane as well as n-butane fuels.
  • 1,1,1,3,3,3-hexafluoropropane is a highly effective fire extinguishant. It is nearly as effective as Halon 251, a chlorofluorocarbon, and it is sufficiently effective, when compared to bromine containing Halons such as Halon 1301 and Halon 1211, that it is preferable by reason of the absence of ozone depletion and other environmental effects of the chlorine and bromine containing Halons.
  • 1.1.1.2.3.3-hexafluoropropane at concentrations in accordance with the method of this invention is well within the range of toxicological safety.
  • the following Examples demonstrate the effective use of hydrofluorocarbon agents in accordance with this invention in mixtures or blends including bromine-containing Halon fire extinguishants.
  • Table 6 reports the actual volume percent in air as observed. Table 6 also reports the calculated weight percent heptafluoropropane in the mixture. In addition. Table 6 also reports the ozone depletion potential ("ODP") for each agent.
  • 1,1,1,3,3,3-hexafluoropropane and pentafluoroethane like the presently employed chlorine and bromine-containing Halons, are nondestructive agents, and are especially useful where cleanup of other media poses a problem.
  • Some of the applications of the hydrofluorocarbons of this invention. are the extinguishing of liquid and gaseous fueled fires, the protection of electrical equipment, ordinary combustibles such as wood, paper and textiles, hazardous solids, and the protection of computer facilities, data processing equipment and control rooms.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fire-Extinguishing By Fire Departments, And Fire-Extinguishing Equipment And Control Thereof (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Measuring Volume Flow (AREA)
  • Fireproofing Substances (AREA)
  • Catalysts (AREA)

Abstract

Des hydrofluorocarbones C2 et C3 fortement fluorurés et saturés sont des agents d'extinction du feu efficaces, économiques et n'endommageant pas la couche d'ozone, utilisés seuls ou dans des mélanges avec d'autres agents d'extinction du feu. Ils se présentent sous forme de systèmes portables et de noyage.
EP90912103A 1989-08-21 1990-08-09 Methodes et melanges pour eteindre le feu, utilisant des fluoropropanes Revoked EP0439579B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US39684189A 1989-08-21 1989-08-21
US07/439,738 US5124053A (en) 1989-08-21 1989-11-21 Fire extinguishing methods and blends utilizing hydrofluorocarbons
PCT/US1990/004467 WO1991002564A1 (fr) 1989-08-21 1990-08-09 Methodes et melanges pour eteindre le feu, utilisant des hydrofluorocarbones
US396841 1995-03-01
US439738 1995-05-12

Publications (3)

Publication Number Publication Date
EP0439579A1 true EP0439579A1 (fr) 1991-08-07
EP0439579A4 EP0439579A4 (en) 1992-03-11
EP0439579B1 EP0439579B1 (fr) 1995-10-25

Family

ID=27015670

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912103A Revoked EP0439579B1 (fr) 1989-08-21 1990-08-09 Methodes et melanges pour eteindre le feu, utilisant des fluoropropanes

Country Status (16)

Country Link
EP (1) EP0439579B1 (fr)
JP (1) JP2580075B2 (fr)
KR (1) KR100189484B1 (fr)
AT (1) ATE129419T1 (fr)
AU (1) AU629975B2 (fr)
BR (1) BR9006888A (fr)
CA (1) CA2023333C (fr)
DE (1) DE69023220T2 (fr)
DK (1) DK0439579T3 (fr)
ES (1) ES2078348T3 (fr)
FI (1) FI103182B (fr)
IL (1) IL95365A (fr)
MX (1) MX172050B (fr)
NO (1) NO177888C (fr)
RU (1) RU2293583C2 (fr)
WO (1) WO1991002564A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5040609A (en) * 1989-10-04 1991-08-20 E. I. Du Pont De Nemours And Company Fire extinguishing composition and process
US5084190A (en) * 1989-11-14 1992-01-28 E. I. Du Pont De Nemours And Company Fire extinguishing composition and process
GB2265309A (en) * 1992-03-21 1993-09-29 Graviner Ltd Kidde Fire extinguishing methods using fluorinated hydrocarbons
AUPQ001599A0 (en) * 1999-04-28 1999-05-20 Cast Centre Pty Ltd Gaseous compositions
US7329786B2 (en) 2001-09-28 2008-02-12 Great Lakes Chemical Corporation Processes for producing CF3CFHCF3
US7223351B2 (en) 2003-04-17 2007-05-29 Great Lakes Chemical Corporation Fire extinguishing mixtures, methods and systems
JP4627045B2 (ja) * 2005-04-27 2011-02-09 セントラル硝子株式会社 金属製造保護ガス

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1926396A (en) * 1930-07-31 1933-09-12 Frigidaire Corp Process of preventing fire by nontoxic substances
GB902590A (en) * 1960-03-22 1962-08-01 Allied Chem Production of heptafluoropropane
GB1132636A (en) * 1965-09-22 1968-11-06 Montedison Spa Improvements in or relating to flame-extinguishing compositions
DE2023552A1 (de) * 1969-05-16 1971-04-01 Montecatim Edison SpA, Mailand (Italien) Feuerloschmittel auf Basis von 1,2 Di bromhexafluorpropan
US3844354A (en) * 1973-07-11 1974-10-29 Dow Chemical Co Halogenated fire extinguishing agent for total flooding system
EP0039471A1 (fr) * 1980-05-05 1981-11-11 Hoechst Aktiengesellschaft Procédé de préparation de 2-chloro-1,1,1,2,3,3,3-heptafluoropropane
JPH05134595A (ja) * 1991-11-11 1993-05-28 Ricoh Co Ltd 教育機器

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5134595A (ja) * 1974-09-17 1976-03-24 Daikin Ind Ltd Kongoshokazai
US4459213A (en) * 1982-12-30 1984-07-10 Secom Co., Ltd. Fire-extinguisher composition
JPH06154B2 (ja) * 1986-09-22 1994-01-05 信越半導体株式会社 塩化シランの消火方法
US4954271A (en) * 1988-10-06 1990-09-04 Tag Investments, Inc. Non-toxic fire extinguishant
FR2662944B2 (fr) * 1989-11-10 1992-09-04 Atochem Nouveau melange azeotropique a bas point d'ebullition a base de fluoroalcanes et ses applications.
KR0178018B1 (ko) * 1990-03-30 1999-03-20 엘리오 거글리일미 무독성 소화제
FR2662947A1 (fr) * 1990-06-08 1991-12-13 Atochem Utilisation d'une composition a base d'halogenoalcanes comme agent extincteur.
FR2662945B1 (fr) * 1990-06-08 1995-03-24 Atochem Utilisation d'un hydrogenofluoroalcane comme agent extincteur.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1926396A (en) * 1930-07-31 1933-09-12 Frigidaire Corp Process of preventing fire by nontoxic substances
GB902590A (en) * 1960-03-22 1962-08-01 Allied Chem Production of heptafluoropropane
GB1132636A (en) * 1965-09-22 1968-11-06 Montedison Spa Improvements in or relating to flame-extinguishing compositions
DE2023552A1 (de) * 1969-05-16 1971-04-01 Montecatim Edison SpA, Mailand (Italien) Feuerloschmittel auf Basis von 1,2 Di bromhexafluorpropan
US3844354A (en) * 1973-07-11 1974-10-29 Dow Chemical Co Halogenated fire extinguishing agent for total flooding system
EP0039471A1 (fr) * 1980-05-05 1981-11-11 Hoechst Aktiengesellschaft Procédé de préparation de 2-chloro-1,1,1,2,3,3,3-heptafluoropropane
JPH05134595A (ja) * 1991-11-11 1993-05-28 Ricoh Co Ltd 教育機器

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9102564A1 *

Also Published As

Publication number Publication date
DE69023220D1 (de) 1995-11-30
KR100189484B1 (en) 1999-06-01
BR9006888A (pt) 1991-10-22
FI103182B1 (fi) 1999-05-14
EP0439579B1 (fr) 1995-10-25
JPH04501228A (ja) 1992-03-05
NO911579D0 (no) 1991-04-22
FI103182B (fi) 1999-05-14
IL95365A0 (en) 1991-06-30
IL95365A (en) 1993-05-13
AU629975B2 (en) 1992-10-15
CA2023333C (fr) 2000-10-03
AU6171990A (en) 1991-04-03
MX172050B (es) 1993-11-30
NO177888B (no) 1995-09-04
NO177888C (no) 1995-12-13
EP0439579A4 (en) 1992-03-11
ATE129419T1 (de) 1995-11-15
DE69023220T2 (de) 1996-04-04
ES2078348T3 (es) 1995-12-16
RU2068718C1 (ru) 1996-11-10
NO911579L (no) 1991-04-22
CA2023333A1 (fr) 1991-02-22
JP2580075B2 (ja) 1997-02-12
DK0439579T3 (da) 1996-01-29
WO1991002564A1 (fr) 1991-03-07
RU2293583C2 (ru) 2007-02-20
FI911915A0 (fi) 1991-04-19

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