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Publication numberUS3276999 A
Publication typeGrant
Publication dateOct 4, 1966
Filing dateJul 9, 1963
Priority dateJul 12, 1962
Also published asDE1278254B, DE1593227A1
Publication numberUS 3276999 A, US 3276999A, US-A-3276999, US3276999 A, US3276999A
InventorsKazia Claude, Wetroff Georges, Petit Roland
Original AssigneePechiney Saint Gobain
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Fire extinguishing process
US 3276999 A
Abstract  available in
Images(2)
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Claims  available in
Description  (OCR text may contain errors)

3,276,999 FllRE EXTINGUISHHNG PRUCESS Roland Petit, Paris, Claude Kaziz, La Courneuve, and Georges Wetroii, Le Thillay, France, assignors to Produits Claimiques Pechiney-Saint-Gobain, Neuillysur=Seine, France N0 Drawing. Filed July 9, 1963, tier. No. 293,378 Claims priority, application France, July 12, 1962, 903,763 t Claims. (Cl. 252-8) This invention relates to a fire extinguishing composition and more particularly to the use of the compound bromo- I-difiuoro-1,1-ethane, alone or in admixture with other components, in the extinguishing of fires and to a new and improved method for the preparation of such fire extinguishing compound.

In the extinguishing of fires, and especially burning hydrocarbon, it is known to make use of halogenated hydrocarbon derivatives, the most effective one to the present being methyl bromide. However, methyl bromide finds numerous objections in a use of this type by reason of its toxicity and dangers which arise in its use. Fire extinguishing characteristics somewhat comparable to methyl bromide, but less toxic than methyl bromide, have been demonstrated by other certain bro-motluorinated derivatives such as bromotrifluoromethane and bromochlorodifiuoromethane but the vapor pressures of these compounds are so high at ambient temperature as to make it necessary to employ air-tight containers of high strength for the housing of such materials. lems arise in the storage of such materials, for use is incapable of being made of low cost, prefabricated containers which are easy to handle.

It is an object of this invention to provide a halogenated hydrocarbon derivative which can be used effectively and efficiently in the extinguishing of fires but which is not subject to the objectionable characteristics of compounds heretofore described and it is a related object to provide a method for the preparation of the halogenated hydrocarbon derivative and the use thereof in extinguishing fires.

More specifically, it is an object of this invention to provide a method for producing a halogenated hydrocarbon derivative which is as effective as methyl bromide in the extinguishing of burning hydrocanbon or other fires; which is relatively non-toxic; which has a vapor pressure sufficiently high at ambient temperature to enable packaging in commercially available, low cost containers; which can be easily stored in containers for use without the build-up of excessive pressures; and which can be used in admixture with other halogenated hydrocarbon r derivatives of the type previously used in fire extinguishers to provide a synergistic eifect which alleviates the undesirable characteristics of such other fire extinguishing compounds without detracting from their fire extinguishing properties.

It has been found, in accordance with the practice of this invention, that the compound bromo-l-difluoro-1,1- ethane has fire extinguishing power which is comparable to that of methyl bromide and which, by reason of its relatively high boiling point of 14-15 C. at atmospheric pressure, is relatively free of the risks of gaseous leakage, explosion or the like, and it is capable of being housed in readily available, low cost containers which can be easily handled in the extinguishing of fires. The compound is also characterized by relative high stability and freedom from decomposition under normal storage conditions.

The bromo-l-d-ifluoro-1,1-ethane can be used alone as a fire extinguishing compound or it can be used in admixture with other halogenated hydrocarbon derivatives, such as the following, which are given by way of Thus delicate prob- Patented Oct. 4, 1966 illustration, but not by way of limitation, but in which the bromo-l-difluoro-l,l-ethane is present to constitute at least 25% by weight and preferably 50% by weight of the compostion:

dichlorodifluoromethane chlorodifluoromethane =bromotrifluoromethane bromochlorodifluoromethane The bromo-l-difluoro-l,l-ethane can be used alone or in admixture with one or more of the other halogenated hydrocarbon derivatives as a fire extinguisher with gaseous propellants, such as nitrogen, carbon dioxide and the like.

Bromo-1-difluoro-l,1-ethane is not a new chemical compound. It has previously been produced by reaction of a bromide with a metallic salt such as the silver salt of difluoropropionic acid at a temperature of about 0 C. It has also been produced by reaction of a hydrobromic acid with vinylidene fluoride whereby a reaction product is secured containing mostly bromo-Z- difluoro-l,1-ethane, with only a small proportion of the desired bromo-l-difluoro-l,lethane. Since the raw materials for these reactions are quite expensive, the described methods for preparation are not considered commercially desirable.

Thus it is also an object of this invention to provide a new and improved means and method for the preparation of bromo-l-difluoro-1,1-ethane of low cost and readily available materials and in high yields.

Brorno-l-difluoro-l,l-ethane can be prepared, in accordance with the improved process of this invention, by a vapor phase reaction of difluoro-1,1-ethane with bromine at a temperature within the range of 350500 C. and preferably at a temperature within the range of 400-450 C.; cooling the reaction product to a temperature below 40 C. and preferably to a temperature within the range of 1S40 C. leaving the desirable bromo-ldifluoro-1,1-ethane and other halogenated hydrocarbon derivatives in the uncondensed state along with formed hydrobromic acid and unreacted bromine; removing the formed hydrobr-omic acid and unreacted bromine; and finally separating the bromo-l-difiuoro-1,l-eth-ane from the remainder by techniques well known to the art, as will hereinafter be described.

For the reaction in the gaseous phase, the ingredients are provided in the molar ratio of 1 mole bromine to 0.5-1.2 moles of difluoro-l,l-ethane and preferably in the ratio of 1 mole bromine to slightly less than 1 mole difiuoro-1,l-ethane. The reaction is carried out for at least 5 seconds and preferably for a period within the range of 10-30 seconds. For the removal of hydrobromic acid and unreacted bromine from the portions which remain uncondensed when the reaction product is cooled to a temperature below 40 C., the uncondensed portions are treated with an alkaline solution, such an aqueous solution of potassium hydroxide. The remainder can thereafter be dried and separated by conventional means to isolate bromo-l-difiuoro-l,l-etl1ane in a relatively pure state.

The fol-lowing examples are given by Way of illustration, but not by way of limitation, of the practice of this invention:

EXAMPLE 1 Preparation of bromo-I-difluor0-1,1-ethane A gaseous mixture of 0.915 mole bromine per mole of difiuoro-l,l-ethane is passed through a glass tube having a length of 40 cm. and an internal diameter of 4 cm. housed within an electrically heated enclosure having a temperature of about 425 C. The flow rate of the gaseous mixture is calculated to provide for exposure to reaction of about 15 seconds.

The gaseous reaction products issuing from the reactor tube are advanced through a jacketed heat exchanger refrigerated with a water coolant to a temperature below 40 C. after which the cooled gases are washed in two wash bottles with a 10% aqueous solution of sodium hydroxide to remove the formed hydrobromic acid and unreacted bromine.

The washed gases are dried by passing them through a drying column packed with pellets of calcium chloride and sodium hydroxide in admixture. The dried gases are condensed in a cooled trap at a temperature of about 80 C. The condensate contains about 84% by weight bromo-1-difluoro-1,1-ethane and about 16% by weight difluorodJ-ethane. The condensate is processed in a fractional distillation column to effect separation of the bromo-l-difluoro-l,l-ethane from the remainder.

The conversion rate of difluoro-1,l-ethane to bromo-ldifluoro-1,1-ethane is in the order of about 75% and the molar yield in bromo-l-d-ifiuoro-l,l-ethane is calculated to be about 85%.

EXAMPLE 2 Fire extinguishing tests For tests of the fire extinguishing power, use was made of a cylindrical tank formed of sheet iron having wall thicknesses of 0.15 cm., an internal diameter of 35 cm., and a height of 10 cm. The cylindrical tank has a capacity for 3 liters of hydrocarbon fluid in the form of F grade petrol having a distillation fraction out which boils between 110 C. and 160 C. and a density of 0.742 at 15 C., which fluid is used as the fuel in the tests.

The fire extinguisher used was a cylindrical container of steel having a capacity of 0.2 liter and which was loaded with 280 grams of bromo-1-difluoro-1,1-ethane and suflicient nitrogen to obtain an internal pressure 8 kg./cm. at ambient temperature.

The petrol was ignited and one minute later the bromo- 1-difluoro-1,1-ethane was supplied onto the fire through a nozzle in the container. The hydrocarbon flame was extinguished within 3 seconds which was less time than required to empty the extinguisher (about 4 seconds).

EXAMPLE 3 An aluminum extinguisher fitted with an impact discharge valve and having a capacity of 0.4 liter was charged with the following fire extinguishing composition:

Grams Bromo-l-difiuoro-l,l-ethane 80 Teepol 26 Glycol 3 2 Water 54 Dichlorodifluoromethane 160 The pressure within the container was in the order of about 2.5 kg./cm. at ambient temperature.

When the fire extinguishing test was conducted, as in 4 Example 2, but with the composition of Example 3, the petrol fire was extinguished within 2.5 seconds while the container continued to spray for an additional 4.5 seconds before becoming emptied.

It will be apparent from the foregoing that we have provided a new and safe process for the extinguishing of fires in which use is made of bromod-difluoro-Llethane as an essential component of the fire extinguishing composition and that We have provided a new and improved method for the commercial production of such brorno-l-difluoro-l,l-ethane.

It will be understood that changes may be made in the details of formulation and operation without departing from the spirit of the invention, especially as defined in the following claims.

We claim:

1. The process for extinguishing fires comprising applying to the -fire a composition, an essential component of which is l-bromo-l,l-difiuoro-ethane present in an amount within the range of 25 to percent by weight of the composition.

2. The process as claimed in claim 1 in which the composition includes a gaseous propellant selected from the group consisting of nitrogen and carbon dioxide.

3. The process as claimed in claim 1 in which the composition include-s a halogenated hydrocarbon selected from the group consisting of dichlorodifluoromethane, chlorodifluoromethane, hromot-rifluoromethane and bromoch-lorodifluoromethane.

4. The process as claimed in claim 1 in which the composition includes a halogenated hydrocarbon selected from the group consisting of dichlorodifluoromethane, chlorodifluoromethane, bromotrifiuoromethane and bromochlorodifluoromethane and a gaseous propellant selected from the group consisting of nitrogen and carbon dioxide.

References Cited by the Examiner UNITED STATES PATENTS 866,437 9/1907 Davidson 2528 2,021,981 11/1935 Bichowsky 252-8 X R 2,653,130 '9/1953 Eiseman 252-8 2,668,419 2/ 1954 Mapes 252-8 XR 2,678,953 5/1954 Conly 2528 XR 2,757,212 7/ 1956 Cleaver et al 260-653 2,897,151 7/1959 Bickett 252 8 2,972,637 2/ 1961 Tullock 260-653 FOREIGN PATENTS 878,854 2/1943 France.

OTHER REFERENCES Freon Technical Bulletin B2, Dupont, Wilmington 98, Del. (1962), page 6 relied upon.

LEON D. ROSDOL, Primary Examiner. JULIUS GREENWALD, Examiner.

M. WEINBLATT, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US866437 *Jan 9, 1907Sep 17, 1907Edward M DavidsonFire-extinguishing compound.
US2021981 *Jun 23, 1930Nov 26, 1935Gen Motors CorpSelf propelling fire extinguishing charge containing a double halogen hydrocarbon compound
US2653130 *May 17, 1951Sep 22, 1953Du PontFire extinguishing composition of cbrf or cfbrcfbr containing cf as a propellant
US2668419 *Oct 26, 1951Feb 9, 1954Specialties Dev CorpFluid carbon dioxide composition
US2678953 *Oct 14, 1950May 18, 1954Douglas Aircraft Co IncMethod of making fluorinated organic bromides and resulting new chemical compounds
US2757212 *Mar 25, 1955Jul 31, 1956Du PontProcess of reacting a halogen, fluorine compound and carbon at temperatures above 1500 deg. c
US2897151 *Sep 7, 1956Jul 28, 1959Superior Products CoVaporizing fire extinguisher fluid
US2972637 *Jun 19, 1958Feb 21, 1961Du PontPreparation of bromofluoromethanes
FR878854A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3479286 *Sep 19, 1966Nov 18, 1969Montedison SpaFlame-extinguishing compositions
US3480545 *Aug 17, 1966Nov 25, 1969Monsanto Res CorpMethod of controlling the spread of fires
US3656553 *May 13, 1970Apr 18, 1972Montedison SpaFlame-extinguishing substance comprising 1,2-dibromohexafluropropane
US3844354 *Jul 11, 1973Oct 29, 1974Dow Chemical CoHalogenated fire extinguishing agent for total flooding system
US4668407 *Dec 23, 1985May 26, 1987Gerard Mark PFire extinguishing composition and method for preparing same
US5055208 *Jan 2, 1991Oct 8, 1991Powsus, Inc.Fire extinguishing compositions
US5093013 *Dec 11, 1989Mar 3, 1992Halocarbon Products CorporationBromotetrafluoroethane, nitrogen, carbon dioxide and carbon tetrafluoride as propellant
WO1992011903A1 *Dec 27, 1991Jul 23, 1992Powsus IncFire-extinguishing compositions
Classifications
U.S. Classification252/8, 570/137, 570/174
International ClassificationA62D1/00, C07C17/10
Cooperative ClassificationC07C17/10, A62D1/0057
European ClassificationC07C17/10, A62D1/00C6