CA2023333C - Fire extinguishing methods and blends utilizing hydrofluorocarbons - Google Patents
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- A—HUMAN NECESSITIES
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- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
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Abstract
Highly fluorinated, saturated, C2 and C3 hydrofluorocarbons are efficient, economical, non-ozone-depleting fire extinguishing agents used alone or in blends with other fire extinguishing agents in total flooding and portable systems.
Description
FIRE EXTINGUISHING METHODS AND BLENDS
UTILIZING HYDROFLUOROCARBONS
BACKGROUND OF THE INVENTION
Field of the Invention.
This invention relates to fire extinguishing methods and blends utilizing higher fluorinated C2 and C3 saturated hydrofluorocarbons.
Description of the Prior Art.
The use of certain bromine, chlorine and iodine-containing halogenated chemical agents for the extinguishment of fires is common. These agents are in general thought to be effective due to their interference with the normal chain reactions responsible for flame propagation. The most widely accepted mechanism far flame suppression is the radical trap mechanism proposed by Fryburg in Review of Literature Pertinent to Fire Extinauishing Aq~ents and to Basic Mechanisms Involved in Their Action, NACA-TN 2102 (1950). The finding that the effectiveness of the halogens are on a molar basis in the order C1<Br<I supports the radical trap mechanism, as reported by Malcom in Vaporizing Fire Extinctuishinq Agents, Report 117, Dept. of Army Engineering Research and Development Laboratories, Fort Bevoir, VA, 1950 (Project- 8-76-04-003). It is thus generally accepted that compounds containing the halogens C1, Br and I act by interfering with free radical or ionic species in the flame and that the effectiveness of these halogens is in the order I>Br>C1.
In contrast, hydrofluorocarbons (i.e., compounds containing only C, H and F atoms) have not heretofore been recognized to display any chemical action in the suppression of combustion. Thus, it is generally A
UTILIZING HYDROFLUOROCARBONS
BACKGROUND OF THE INVENTION
Field of the Invention.
This invention relates to fire extinguishing methods and blends utilizing higher fluorinated C2 and C3 saturated hydrofluorocarbons.
Description of the Prior Art.
The use of certain bromine, chlorine and iodine-containing halogenated chemical agents for the extinguishment of fires is common. These agents are in general thought to be effective due to their interference with the normal chain reactions responsible for flame propagation. The most widely accepted mechanism far flame suppression is the radical trap mechanism proposed by Fryburg in Review of Literature Pertinent to Fire Extinauishing Aq~ents and to Basic Mechanisms Involved in Their Action, NACA-TN 2102 (1950). The finding that the effectiveness of the halogens are on a molar basis in the order C1<Br<I supports the radical trap mechanism, as reported by Malcom in Vaporizing Fire Extinctuishinq Agents, Report 117, Dept. of Army Engineering Research and Development Laboratories, Fort Bevoir, VA, 1950 (Project- 8-76-04-003). It is thus generally accepted that compounds containing the halogens C1, Br and I act by interfering with free radical or ionic species in the flame and that the effectiveness of these halogens is in the order I>Br>C1.
In contrast, hydrofluorocarbons (i.e., compounds containing only C, H and F atoms) have not heretofore been recognized to display any chemical action in the suppression of combustion. Thus, it is generally A
thought that to be effective as a fire extinguishing agent, a compound must contain C1, Br or I.
The use of 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 (CF3Br), Halori 1211 (CF2BrCl) and Halon 2402 (CFZBrCFZBr). The effectiveness of these three volatile bromine-containing compounds in extinguishing fires has been described in U.S. Patent 4,014,799 to Owens. Although not employed commercially, certain chlorine-containing compounds are also known to be effective extinguishing agents, for example Halon 251 (CF3CF2C1) as described by Larsen in U.S. Patent 3,844,354.
Although the above named 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 A
environmentally safe.
The use of 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 (CF3Br), Halori 1211 (CF2BrCl) and Halon 2402 (CFZBrCFZBr). The effectiveness of these three volatile bromine-containing compounds in extinguishing fires has been described in U.S. Patent 4,014,799 to Owens. Although not employed commercially, certain chlorine-containing compounds are also known to be effective extinguishing agents, for example Halon 251 (CF3CF2C1) as described by Larsen in U.S. Patent 3,844,354.
Although the above named 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 A
environmentally safe.
SUMMARY OF THE INVENTION
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 CZ or C3 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 CxHyFz, 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 heptaf loot opropane ( CF3CHFCF;) , 1, 1, 1, 3, 3, 3-hFx.afluorapropane (CF3CH~CF3) , 1, 1, 1,'2, 3, 3-hexafluoropropar_e (CF3CHFCHF2) and pentafluoroethane (CF3CHF2) . These hydrofluorocarbons may be used alone, in admixture with each other or as blends with other fire extinguishing agents. Generally, the agents of this invention are employed at concentrations lying in the range of about 3 to 15%, preferably 5 to 10%, on a v/v basis.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, saturated higher fluorinated C2 and C3 hydrofluorocarbons have been found to be effective fire extinguishants at concentrations safe for use. However, because such hydrofluorocarbons contain no bromine or chlorine, they have an ozone depletion potential of zero. Furthermore, since 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 CxHyFz, 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 (CF3CHFCF3), 1,1,1,3,3,3-hexafluoro-propane (CF3CHZCF3), 1,1,1,2,3,3-hexafluoropropane ( CF3CHFCHF2 ) , and pentaf luoroethane ( CF3CHFz ) .
These compounds may be used alone or in admixture with each other or in blends with other fire extinguishing agents. Among the other agents with which the hydrofluorocarbons of this invention may be blended are chlorine and/or bromine containing compounds such as Halon 1301 (CF3Br), Halon 1211 (CF2BrCl), Halon 2402 (CFZBrCFZBr) , Halon 251 (CF3CFZC1) and CF3CHFBr. Mixtures of heptafluoropropane and Halon 1201 (CF2HBr) are especially preferred because the compounds have similar vapor pressures over a wide range of temperatures and therefore the composition of the mixture remains relatively constant during discharge or other application.
Where the 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.
The hydrofluorocarbon compounds used in accordance with this invention are non-toxic and are economical to manufacture. For example, heptafluoropropane may be conveniently produced via the reaction of commercially available hexafluoropropene (CF3CF=CF2) with anhydrous HF as described in U.K. Patent 902,590. Similarly, 1,1,1,3,3,3-hexafluoropropane may be synthesized by reacting anhydrous HF with pentaf luoropropene ( CF3CH=CFz ) .
1,1,1,2,3,3-hexafluoropropane may be obtained by hydrogenation of hexafluoropropene (CF3CF=CF2).
Pentafluoroethane may be obtained by the addition of hydrofluoric acid to tetrafluoroethylene (CF2=CFZ) .
The saturated highly fluorinated CZ and C3 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. In general, however, best results are achieved where the hydrofluorocarbons or mixtures and blends thereof are employed at a level of at least about 3% (v/v). Where hydrofluorocarbons alone are employed, best results are achieved with agent levels of at least about 5% (v/v). Likewise, 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. Thus, 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. In accordance with a total flooding system apparatus, 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. Thus, as is known to those skilled in the art, the fire extinguishant may be pressurized with nitrogen or other inert gas at up to about 600 psig at ambient conditions.
Alternatively, 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. Hydrofluorocarbon containing systems in accordance with this invention may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions.
Practice of the present invention is illustrated by the following Examples, which are presented for purposes of illustration but not of limitation.
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 _8_ tested and an inlet near the bottom to admit air. To test the agent, 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 CF3CHFBr are given in Table 1.
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 same agents are also given in Table 1.
Table 1 Extinguishment Time (seconds) for 6.6 % v/v Agent Agent Lighter fluid n-Heptane CF3CHFCF3 1. 6 1. 6 CF3Br 0 . 8 1. 4 (Halon 1301) CFZBrCl 1.3 1.7 (Halon 1211) CF3CHFBr 1. 0 1. 7 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 _ g -an n-heptane flame and nearly effective as the other agents in extinguishing lighter fluid flames.
Levels of about 5-l0% 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.
Dynamic burn test data for heptafluoropropane and 1,1,1,2,3,3-hexafluoropropane were obtained using the cup burner test procedure in which air and n-butane are continuously supplied to a flame produced in a glass cup burner. Vapor of the agent to be tested was mixed with air and introduced to the flame, with the concentration of agent being slowly increased until the flow was just sufficient to cause extinction of the flame. Data were obtained in this manner for heptafluoropropane and 1,1,1,2,3,3-hexafluoropropane and, for comparative purposes, for the following other Halon agents: Halon 1301 (CF3Br) ; Halon 1211 (CFZBrCl) ; Halon 251 (CF3CFZC1) ;
Halon 25 (CF3CFZH); and Halon 14 (CF4). The percent of each agent in air (v/v) required to extinguish the flame is given in Table 2.
Extinguishment n-Butane Diffusion of Flames Air flow Agent Required Agent In Air Agent cc/min cc/min o v/v Halon 1301 16,200 396 2.4 ( CF3Br ) Halon 1211 16,200 437 2.7 ( CFZBrCl ) Halon 251 16,200 963 5.9 ( CF3CF2C1 ) CF3CHFCF3 16, 200 976 6. 0 CF3CHFCHFZ 16,200 1312 8.1 Halon 25 16,200 1409 8.7 ( CF3CFZH
) Halon 14 16,200 2291 14.1 (CF4) Heptafluoropropane Halon 1211 and Halon 1301, and Halon were used extinguish n-heptane 251 to diffusion flames using the method Example 4. Test data are of reported in able 3.
T
Extinguishment of n-Heptane Diffusion Flames Air flow Agent Required Agent In Air Agent cc/min cc/min v/v Halon 1301 16,200 510 3.1 ( CF3Br ) Halon 1211 16,200 546 3.4 ( CFZBrC 1 ) Halon 251 16,200 1,006 6.2 ( CF3CFZC1 ) CF3CHFCF3 16, 200 1, 033 6. 4 Halon 25 16,200 1,506 9.3 ( CF3CFZH ) The dynamic test data reported in Tables 2 and 3 demonstrate that use of 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 (CF4). Moreover, 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. While bromine and chlorine-containing agents such as Halon 1301 and Halon 1211 are somewhat more effective than the hydrofluoro-carbon agents under the cup burner test, the use of the agents in accordance with this invention remains highly effective and their use avoids the significant environmental handicaps encountered with chlorine and bromine containing Halons such as Halon 1301, Halon 1211, and Halon 251.
Static box flame extinguishment data were obtained for 1,1,1,3,3,3-hexafluoropropane with a 35.2 litre test enclosure using the procedure of Example 1.
In addition to 1,1,1,3,3,3-hexafluoropropane, for comparative purposes, Halon 1301, Halon 1211 and Halon 251 were also tested. All agents were delivered at a test concentration of 5.5% (v/v).
Extinguishment Time (Seconds) for 5.5% (v/v) Agent Aaent Extinction Times) Halon 1301 1.02 (CF3Br) 15 Halon 1211 1.76 ( CFZBrCl ) Halon 251 2.15 ( CF3CF2C1 ) CF3CHZCF3 2 . 9 8 The data of Table 4 demonstrates that 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, 25 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.
30 In addition to being a highly effective agent for extinguishing fires, 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.
35 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.
Dynamic test data using the cup burner procedure of Example 4 were obtained for various mixtures of heptafluoropropane and Halon 1201 (CF2HBr). Air and a mixture of the agents were continuously supplied to an n-heptane diffusion flame produced in a glass cup burner.
For a given heptafluoropropane flow, the flow of CFZHBr was slowly increased until the flow was just sufficient to cause extinction of the flame. The experiment was repeated at various heptafluoropropane flow rates, and the results are reported in Table 6.
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. ODP data for Halon 1201 was calculated in the following manner. ODP's for pure compounds were calculated by the following formula:
ODP = A E P [(#C1)B + C(#Br)] D(#C-1) In this expression, P is the photolysis factor. P=1.0 if there are no special structural features which make the molecule subject to tropospheric photolysis. Otherwise, P=F, G, or H, as indicated in the table of constants, Table 5 below.
CONSTANT NAME VALUE
F Photolysis factor for geminal Br-C-C1 0.180 G Photolysis factor for geminal Br-C-Br 0.015 H Photolysis factor for adjacent BR-C-C-Br0.370 A Normalizing constant 0.446 B Exponent for chlorine term 0.740 C Multiplier for bromine 32.000 term D Constant for carbon term 1.120 E Hydrogen factor [=1.0 for no H's] .0625 ODP's for the mixtures were obtained by multiplying the weight percent of the Halon 1201 by the ODP of pure Halon 1201.
Extinguishment of n-Heptane Diffusion Flames CF3CHFCF3 / CF2HBr Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF3CHFCF3 CF2HBr CF3CHFCF3 CF2HBr Vol % CF3CHFCF3 ODP
0 1380 0 4.0 4.0 0 0.89 164 489 1.0 3.0 4.0 30.1 0.62 353 357 2.2 2.2 4.4 56.5 0.39 533 216 3.3 1.3 4.6 76.6 0.21 705 122 4.3 0.8 5.1 87.4 0.11 869 39 5.4 0.2 5.6 97.2 0.02 1042 0 6.4 0 6.4 100.0 0.00 These data demonstrate that effective flame extinguishment may be obtained with mixtures of heptafluoropropane and Halon 1201 and that the ODP of Halon 1201 can be materially reduced by providing heptafluoropropane therewith.
Tables 7, 8, 9 and 10 report diffusion flame extinguishment data obtained using the method of Example 7 for the following agent mixtures:
Table 7 - heptafluoropropane and Halon 1211 ( CF2BrC1 ) ( CF3Br ) Table 8 - heptafluoropropane and Halon 1301 Table 9 - pentafluoroethane and Halon 1201 ( CFZHBr ) Table 10- 1,1,1,2,3,3-hexafluoropropane and Halon 1201 (CFZHBr) These Tables also contain ODP data for pure Halons 1211 and 1301 as reported by the Lawrence Livermore Research Laboratories. ODP's for Halon 1201 were calculated using the method given above, and ODP's for the mixtures were obtained by multiplying the weight percent of the Halon agent by the ODP of the pure Halon.
Extinguishment of n-Heptane Diffusion Flames CF3CHFCF3 / CFZBrCl Mixtures Flow at 2 5 Extinguishment cc/min Volume ~ in Air Total Weight CF3CHFCF3 CFZBrClCF3CHFCF3 CFZBrClVol $ CF3CHFCF3 ODP
0 546 0 3.4 3.4 0 2.64 164 437 1.0 2.7 3.7 27.5 1.91 262 378 1.6 . 2.3 3.9 41.7 1.54 353 328 2.2 2.0 4.2 53.1 1.24 533 210 3.3 1.3 4.6 72.5 0.73 705 109 4.3 0.7 5.0 86.3 0.36 869 44 5.4 0.2 5.6 94.9 0.13 1042 0 6.4 0 6.4 100.0 0.00 Extinguishment of n-Heptane Diffusion Flames CF3CHFCF3 / CF3Br Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF3CHFCF3CF3Br CF3CHFCF3 CF3Br Vol % CF3CHFCF3 ODP
0 510 0 3.1 3.1 0 14.28 164 422 1.0 2.6 3.6 30.4 9.93 262 334 1.6 2.1 3.7 46.4 7.65 353 317 2.2 1.9 4.1 57.1 6.13 533 246 3.3 1.5 4.8 71.6 4.06 705 98 4.3 0.6 4.9 89.2 1.54 869 51 5.4 0.3 5.7 95.4 0.66 943 24 5.8 0.1 6.0 98.5 0.21 1042 0 6.4 0 6.4 100.0 0.00 Extinguishment of n-Heptane Diffusion Flames CF3CFZH / CF2HBr Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF,CF.,H CF,.HBr CF_CF..H CF_HBr Vol ~: CF_CF_H OnP
0 1380 0 4.0 4.0 0 0.89 196 526 1.2 3.2 4.4 25.6 0.66 314 470 1.9 2.9 4.8 37.5 0.56 421 423 2.6 2.6 5.2 47.7 0.46 637 338 3.9 2.1 6.0 63.0 0.33 1039 109 6.4 0.7 7.1 89.4 0.09 1509 0 9.3 0 9.3 100.0 0.00 Extinguishment of n-Heptane Diffusion Flames CF3CHFCFZH / CFZHBr Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF3CHFCFZH CFZHBrCF3CHFCFZH CFZHBr Vol CF3CHFCF2HODP
%
0 1380 0 4.0 4.0 0 0.89 196 508 1.2 3.1 4.3 30.8 0.62 421 423 2.6 2.6 5.2 53.7 0.41 637 367 3.9 2.3 6.2 66.3 0.30 843 207 5.2 1.3 6.5 82.1 0.16 The data of Tables 7 through 10 demonstrate that various mixtures of hydrofluorocarbons in accordance with this invention with chlorine and/or bromine-containing Halons are effective flame extinguishment agents and that significant reductions in ODP of the chlorine and/or bromine containing materials can be obtained by admixture thereof with hydrofluorocarbons in accordance with this invention.
Saturated higher fluorinated CZ and~C3 hydrofluorocarbons such as heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 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.
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 CZ or C3 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 CxHyFz, 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 heptaf loot opropane ( CF3CHFCF;) , 1, 1, 1, 3, 3, 3-hFx.afluorapropane (CF3CH~CF3) , 1, 1, 1,'2, 3, 3-hexafluoropropar_e (CF3CHFCHF2) and pentafluoroethane (CF3CHF2) . These hydrofluorocarbons may be used alone, in admixture with each other or as blends with other fire extinguishing agents. Generally, the agents of this invention are employed at concentrations lying in the range of about 3 to 15%, preferably 5 to 10%, on a v/v basis.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, saturated higher fluorinated C2 and C3 hydrofluorocarbons have been found to be effective fire extinguishants at concentrations safe for use. However, because such hydrofluorocarbons contain no bromine or chlorine, they have an ozone depletion potential of zero. Furthermore, since 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 CxHyFz, 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 (CF3CHFCF3), 1,1,1,3,3,3-hexafluoro-propane (CF3CHZCF3), 1,1,1,2,3,3-hexafluoropropane ( CF3CHFCHF2 ) , and pentaf luoroethane ( CF3CHFz ) .
These compounds may be used alone or in admixture with each other or in blends with other fire extinguishing agents. Among the other agents with which the hydrofluorocarbons of this invention may be blended are chlorine and/or bromine containing compounds such as Halon 1301 (CF3Br), Halon 1211 (CF2BrCl), Halon 2402 (CFZBrCFZBr) , Halon 251 (CF3CFZC1) and CF3CHFBr. Mixtures of heptafluoropropane and Halon 1201 (CF2HBr) are especially preferred because the compounds have similar vapor pressures over a wide range of temperatures and therefore the composition of the mixture remains relatively constant during discharge or other application.
Where the 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.
The hydrofluorocarbon compounds used in accordance with this invention are non-toxic and are economical to manufacture. For example, heptafluoropropane may be conveniently produced via the reaction of commercially available hexafluoropropene (CF3CF=CF2) with anhydrous HF as described in U.K. Patent 902,590. Similarly, 1,1,1,3,3,3-hexafluoropropane may be synthesized by reacting anhydrous HF with pentaf luoropropene ( CF3CH=CFz ) .
1,1,1,2,3,3-hexafluoropropane may be obtained by hydrogenation of hexafluoropropene (CF3CF=CF2).
Pentafluoroethane may be obtained by the addition of hydrofluoric acid to tetrafluoroethylene (CF2=CFZ) .
The saturated highly fluorinated CZ and C3 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. In general, however, best results are achieved where the hydrofluorocarbons or mixtures and blends thereof are employed at a level of at least about 3% (v/v). Where hydrofluorocarbons alone are employed, best results are achieved with agent levels of at least about 5% (v/v). Likewise, 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. Thus, 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. In accordance with a total flooding system apparatus, 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. Thus, as is known to those skilled in the art, the fire extinguishant may be pressurized with nitrogen or other inert gas at up to about 600 psig at ambient conditions.
Alternatively, 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. Hydrofluorocarbon containing systems in accordance with this invention may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions.
Practice of the present invention is illustrated by the following Examples, which are presented for purposes of illustration but not of limitation.
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 _8_ tested and an inlet near the bottom to admit air. To test the agent, 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 CF3CHFBr are given in Table 1.
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 same agents are also given in Table 1.
Table 1 Extinguishment Time (seconds) for 6.6 % v/v Agent Agent Lighter fluid n-Heptane CF3CHFCF3 1. 6 1. 6 CF3Br 0 . 8 1. 4 (Halon 1301) CFZBrCl 1.3 1.7 (Halon 1211) CF3CHFBr 1. 0 1. 7 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 _ g -an n-heptane flame and nearly effective as the other agents in extinguishing lighter fluid flames.
Levels of about 5-l0% 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.
Dynamic burn test data for heptafluoropropane and 1,1,1,2,3,3-hexafluoropropane were obtained using the cup burner test procedure in which air and n-butane are continuously supplied to a flame produced in a glass cup burner. Vapor of the agent to be tested was mixed with air and introduced to the flame, with the concentration of agent being slowly increased until the flow was just sufficient to cause extinction of the flame. Data were obtained in this manner for heptafluoropropane and 1,1,1,2,3,3-hexafluoropropane and, for comparative purposes, for the following other Halon agents: Halon 1301 (CF3Br) ; Halon 1211 (CFZBrCl) ; Halon 251 (CF3CFZC1) ;
Halon 25 (CF3CFZH); and Halon 14 (CF4). The percent of each agent in air (v/v) required to extinguish the flame is given in Table 2.
Extinguishment n-Butane Diffusion of Flames Air flow Agent Required Agent In Air Agent cc/min cc/min o v/v Halon 1301 16,200 396 2.4 ( CF3Br ) Halon 1211 16,200 437 2.7 ( CFZBrCl ) Halon 251 16,200 963 5.9 ( CF3CF2C1 ) CF3CHFCF3 16, 200 976 6. 0 CF3CHFCHFZ 16,200 1312 8.1 Halon 25 16,200 1409 8.7 ( CF3CFZH
) Halon 14 16,200 2291 14.1 (CF4) Heptafluoropropane Halon 1211 and Halon 1301, and Halon were used extinguish n-heptane 251 to diffusion flames using the method Example 4. Test data are of reported in able 3.
T
Extinguishment of n-Heptane Diffusion Flames Air flow Agent Required Agent In Air Agent cc/min cc/min v/v Halon 1301 16,200 510 3.1 ( CF3Br ) Halon 1211 16,200 546 3.4 ( CFZBrC 1 ) Halon 251 16,200 1,006 6.2 ( CF3CFZC1 ) CF3CHFCF3 16, 200 1, 033 6. 4 Halon 25 16,200 1,506 9.3 ( CF3CFZH ) The dynamic test data reported in Tables 2 and 3 demonstrate that use of 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 (CF4). Moreover, 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. While bromine and chlorine-containing agents such as Halon 1301 and Halon 1211 are somewhat more effective than the hydrofluoro-carbon agents under the cup burner test, the use of the agents in accordance with this invention remains highly effective and their use avoids the significant environmental handicaps encountered with chlorine and bromine containing Halons such as Halon 1301, Halon 1211, and Halon 251.
Static box flame extinguishment data were obtained for 1,1,1,3,3,3-hexafluoropropane with a 35.2 litre test enclosure using the procedure of Example 1.
In addition to 1,1,1,3,3,3-hexafluoropropane, for comparative purposes, Halon 1301, Halon 1211 and Halon 251 were also tested. All agents were delivered at a test concentration of 5.5% (v/v).
Extinguishment Time (Seconds) for 5.5% (v/v) Agent Aaent Extinction Times) Halon 1301 1.02 (CF3Br) 15 Halon 1211 1.76 ( CFZBrCl ) Halon 251 2.15 ( CF3CF2C1 ) CF3CHZCF3 2 . 9 8 The data of Table 4 demonstrates that 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, 25 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.
30 In addition to being a highly effective agent for extinguishing fires, 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.
35 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.
Dynamic test data using the cup burner procedure of Example 4 were obtained for various mixtures of heptafluoropropane and Halon 1201 (CF2HBr). Air and a mixture of the agents were continuously supplied to an n-heptane diffusion flame produced in a glass cup burner.
For a given heptafluoropropane flow, the flow of CFZHBr was slowly increased until the flow was just sufficient to cause extinction of the flame. The experiment was repeated at various heptafluoropropane flow rates, and the results are reported in Table 6.
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. ODP data for Halon 1201 was calculated in the following manner. ODP's for pure compounds were calculated by the following formula:
ODP = A E P [(#C1)B + C(#Br)] D(#C-1) In this expression, P is the photolysis factor. P=1.0 if there are no special structural features which make the molecule subject to tropospheric photolysis. Otherwise, P=F, G, or H, as indicated in the table of constants, Table 5 below.
CONSTANT NAME VALUE
F Photolysis factor for geminal Br-C-C1 0.180 G Photolysis factor for geminal Br-C-Br 0.015 H Photolysis factor for adjacent BR-C-C-Br0.370 A Normalizing constant 0.446 B Exponent for chlorine term 0.740 C Multiplier for bromine 32.000 term D Constant for carbon term 1.120 E Hydrogen factor [=1.0 for no H's] .0625 ODP's for the mixtures were obtained by multiplying the weight percent of the Halon 1201 by the ODP of pure Halon 1201.
Extinguishment of n-Heptane Diffusion Flames CF3CHFCF3 / CF2HBr Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF3CHFCF3 CF2HBr CF3CHFCF3 CF2HBr Vol % CF3CHFCF3 ODP
0 1380 0 4.0 4.0 0 0.89 164 489 1.0 3.0 4.0 30.1 0.62 353 357 2.2 2.2 4.4 56.5 0.39 533 216 3.3 1.3 4.6 76.6 0.21 705 122 4.3 0.8 5.1 87.4 0.11 869 39 5.4 0.2 5.6 97.2 0.02 1042 0 6.4 0 6.4 100.0 0.00 These data demonstrate that effective flame extinguishment may be obtained with mixtures of heptafluoropropane and Halon 1201 and that the ODP of Halon 1201 can be materially reduced by providing heptafluoropropane therewith.
Tables 7, 8, 9 and 10 report diffusion flame extinguishment data obtained using the method of Example 7 for the following agent mixtures:
Table 7 - heptafluoropropane and Halon 1211 ( CF2BrC1 ) ( CF3Br ) Table 8 - heptafluoropropane and Halon 1301 Table 9 - pentafluoroethane and Halon 1201 ( CFZHBr ) Table 10- 1,1,1,2,3,3-hexafluoropropane and Halon 1201 (CFZHBr) These Tables also contain ODP data for pure Halons 1211 and 1301 as reported by the Lawrence Livermore Research Laboratories. ODP's for Halon 1201 were calculated using the method given above, and ODP's for the mixtures were obtained by multiplying the weight percent of the Halon agent by the ODP of the pure Halon.
Extinguishment of n-Heptane Diffusion Flames CF3CHFCF3 / CFZBrCl Mixtures Flow at 2 5 Extinguishment cc/min Volume ~ in Air Total Weight CF3CHFCF3 CFZBrClCF3CHFCF3 CFZBrClVol $ CF3CHFCF3 ODP
0 546 0 3.4 3.4 0 2.64 164 437 1.0 2.7 3.7 27.5 1.91 262 378 1.6 . 2.3 3.9 41.7 1.54 353 328 2.2 2.0 4.2 53.1 1.24 533 210 3.3 1.3 4.6 72.5 0.73 705 109 4.3 0.7 5.0 86.3 0.36 869 44 5.4 0.2 5.6 94.9 0.13 1042 0 6.4 0 6.4 100.0 0.00 Extinguishment of n-Heptane Diffusion Flames CF3CHFCF3 / CF3Br Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF3CHFCF3CF3Br CF3CHFCF3 CF3Br Vol % CF3CHFCF3 ODP
0 510 0 3.1 3.1 0 14.28 164 422 1.0 2.6 3.6 30.4 9.93 262 334 1.6 2.1 3.7 46.4 7.65 353 317 2.2 1.9 4.1 57.1 6.13 533 246 3.3 1.5 4.8 71.6 4.06 705 98 4.3 0.6 4.9 89.2 1.54 869 51 5.4 0.3 5.7 95.4 0.66 943 24 5.8 0.1 6.0 98.5 0.21 1042 0 6.4 0 6.4 100.0 0.00 Extinguishment of n-Heptane Diffusion Flames CF3CFZH / CF2HBr Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF,CF.,H CF,.HBr CF_CF..H CF_HBr Vol ~: CF_CF_H OnP
0 1380 0 4.0 4.0 0 0.89 196 526 1.2 3.2 4.4 25.6 0.66 314 470 1.9 2.9 4.8 37.5 0.56 421 423 2.6 2.6 5.2 47.7 0.46 637 338 3.9 2.1 6.0 63.0 0.33 1039 109 6.4 0.7 7.1 89.4 0.09 1509 0 9.3 0 9.3 100.0 0.00 Extinguishment of n-Heptane Diffusion Flames CF3CHFCFZH / CFZHBr Mixtures Flow at Extinguishment cc/min Volume % in Air Total Weight %
CF3CHFCFZH CFZHBrCF3CHFCFZH CFZHBr Vol CF3CHFCF2HODP
%
0 1380 0 4.0 4.0 0 0.89 196 508 1.2 3.1 4.3 30.8 0.62 421 423 2.6 2.6 5.2 53.7 0.41 637 367 3.9 2.3 6.2 66.3 0.30 843 207 5.2 1.3 6.5 82.1 0.16 The data of Tables 7 through 10 demonstrate that various mixtures of hydrofluorocarbons in accordance with this invention with chlorine and/or bromine-containing Halons are effective flame extinguishment agents and that significant reductions in ODP of the chlorine and/or bromine containing materials can be obtained by admixture thereof with hydrofluorocarbons in accordance with this invention.
Saturated higher fluorinated CZ and~C3 hydrofluorocarbons such as heptafluoropropane, 1,1,1,2,3,3-hexafluoropropane, 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.
Claims (14)
1. A method for extinguishing a fire comprising the steps of introducing to the fire a fire extinguishing concentration of one or more compounds of the formula C x H y F z, where x is 3, y is 1 or 2, and z is 6 or 7; and maintaining the concentration of the compound until the fire is extinguished.
2. A method, as claimed in claim 1, wherein the compound is employed at a level of less than about 15% (v/v).
3. A method, as claimed in Claim 1, wherein the extinguishing concentration of the compound is from about 5 to 10% (v/v).
4. A method , as claimed in Claim 1, wherein the compound is employed in a total flooding system.
5. A method , as claimed in Claim 1, wherein the compound is employed in a portable extinguishing system.
6. The use of one or more compounds of the formula C x H y F z, where x is 3, y is 1 or 2, and z is 6 or 7; as a nondestructive fire extinguishing agent.
7. A method as claimed in claim 1, wherein the compound is a member selected from the group consisting of heptafluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,3,3-hexafluoro-propane, and mixtures thereof.
8. A method, as claimed in any of claims 1 to 5 or 7, wherein the compound is heptafluoropropane.
9. A method as claimed in claim 8, wherein the heptafluoropropane is employed at a concentration of about 5 to 15% (v/v).
10. A method for extinguishing a fire comprising the steps of:
introducing to the fire a fire extinguishing concentration of a mixture comprising:
one or more compounds of the formula C x H y F z, where x is 3, y is 1 or 2, and z is 6 or 7; and one or more chlorine and/or bromine containing fire extinguishing agent selected from the group consisting of CF3Br, CF2BrCl, CF3CF2Cl, CF2BrCF2Br, CF2HBr and CF3CHFBr, wherein the compound is present in the mixture at a level of at least about 10% by weight of the mixture; and maintaining the concentration of the mixture until the fire is extinguished.
introducing to the fire a fire extinguishing concentration of a mixture comprising:
one or more compounds of the formula C x H y F z, where x is 3, y is 1 or 2, and z is 6 or 7; and one or more chlorine and/or bromine containing fire extinguishing agent selected from the group consisting of CF3Br, CF2BrCl, CF3CF2Cl, CF2BrCF2Br, CF2HBr and CF3CHFBr, wherein the compound is present in the mixture at a level of at least about 10% by weight of the mixture; and maintaining the concentration of the mixture until the fire is extinguished.
11. A method, as claimed in claim 10, wherein the fire extinguishing concentration of the mixture is about 3 to 15% (v/v).
12. A fire extinguishing mixture comprising:
at least about 10%, by weight of the mixture, of one or more compounds of the formula C x H y F z, where x is 3, y is 1 or 2, and z is 6 or 7; and no more than about 90%, by weight of the mixture, of one or more chlorine and/or bromine containing fire extinguishing agents selected from the group consisting of CF3Br, CF2BrCl, CF3CF2Cl, CF2BrCF2Br, CF2HBr and CF3CHFBr.
at least about 10%, by weight of the mixture, of one or more compounds of the formula C x H y F z, where x is 3, y is 1 or 2, and z is 6 or 7; and no more than about 90%, by weight of the mixture, of one or more chlorine and/or bromine containing fire extinguishing agents selected from the group consisting of CF3Br, CF2BrCl, CF3CF2Cl, CF2BrCF2Br, CF2HBr and CF3CHFBr.
13. A fire extinguishing mixture, as claimed in claim 12, wherein the compound is heptafluoropropane and the member is CF2HBr.
14. A use as claimed in claim 6, wherein the compound is heptafluoropropane.
Applications Claiming Priority (4)
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|---|---|---|---|
| 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 |
| US439,738 | 1989-11-21 | ||
| US396,841 | 1995-03-01 |
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| CA2023333A1 CA2023333A1 (en) | 1991-02-22 |
| CA2023333C true CA2023333C (en) | 2000-10-03 |
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| CA002023333A Expired - Lifetime CA2023333C (en) | 1989-08-21 | 1990-08-15 | Fire extinguishing methods and blends utilizing hydrofluorocarbons |
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| JP (1) | JP2580075B2 (en) |
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| 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 (en) * | 2005-04-27 | 2011-02-09 | セントラル硝子株式会社 | Metal production protective gas |
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| 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 |
| NL7006794A (en) * | 1969-05-16 | 1970-11-18 | ||
| US3844354A (en) * | 1973-07-11 | 1974-10-29 | Dow Chemical Co | Halogenated fire extinguishing agent for total flooding system |
| JPS5134595A (en) * | 1974-09-17 | 1976-03-24 | Daikin Ind Ltd | KONGOSHOKAZAI |
| DE3017154A1 (en) * | 1980-05-05 | 1981-11-12 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING 2-CHLORINE-1,1,1,2,3,3,3, -HEPTAFLUOR-PROPANE |
| US4459213A (en) * | 1982-12-30 | 1984-07-10 | Secom Co., Ltd. | Fire-extinguisher composition |
| JPH06154B2 (en) * | 1986-09-22 | 1994-01-05 | 信越半導体株式会社 | Extinguishing method of silane chloride |
| US4954271A (en) * | 1988-10-06 | 1990-09-04 | Tag Investments, Inc. | Non-toxic fire extinguishant |
| FR2662944B2 (en) * | 1989-11-10 | 1992-09-04 | Atochem | NEW AZEOTROPIC MIXTURE WITH LOW BOILING POINT BASED ON FLUOROALKANES AND ITS APPLICATIONS. |
| KR0178018B1 (en) * | 1990-03-30 | 1999-03-20 | 엘리오 거글리일미 | Non-toxic fire extinguishant |
| FR2662947A1 (en) * | 1990-06-08 | 1991-12-13 | Atochem | USE OF A COMPOSITION BASED ON HALOGENOALKANES AS EXTINGUISHING AGENT. |
| FR2662945B1 (en) * | 1990-06-08 | 1995-03-24 | Atochem | USE OF A HYDROGENOFLUOROALKANE AS AN EXTINGUISHING AGENT. |
| JPH05134595A (en) * | 1991-11-11 | 1993-05-28 | Ricoh Co Ltd | Teaching equipment |
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- 1990-08-09 JP JP2511655A patent/JP2580075B2/en not_active Expired - Lifetime
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- 1990-08-09 AT AT90912103T patent/ATE129419T1/en active
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| DE69023220D1 (en) | 1995-11-30 |
| KR100189484B1 (en) | 1999-06-01 |
| BR9006888A (en) | 1991-10-22 |
| FI103182B1 (en) | 1999-05-14 |
| EP0439579B1 (en) | 1995-10-25 |
| JPH04501228A (en) | 1992-03-05 |
| NO911579D0 (en) | 1991-04-22 |
| FI103182B (en) | 1999-05-14 |
| IL95365A0 (en) | 1991-06-30 |
| EP0439579A1 (en) | 1991-08-07 |
| IL95365A (en) | 1993-05-13 |
| AU629975B2 (en) | 1992-10-15 |
| AU6171990A (en) | 1991-04-03 |
| MX172050B (en) | 1993-11-30 |
| NO177888B (en) | 1995-09-04 |
| NO177888C (en) | 1995-12-13 |
| EP0439579A4 (en) | 1992-03-11 |
| ATE129419T1 (en) | 1995-11-15 |
| DE69023220T2 (en) | 1996-04-04 |
| ES2078348T3 (en) | 1995-12-16 |
| RU2068718C1 (en) | 1996-11-10 |
| NO911579L (en) | 1991-04-22 |
| CA2023333A1 (en) | 1991-02-22 |
| JP2580075B2 (en) | 1997-02-12 |
| DK0439579T3 (en) | 1996-01-29 |
| WO1991002564A1 (en) | 1991-03-07 |
| RU2293583C2 (en) | 2007-02-20 |
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