Environmentally benign non-toxic fire flooding agents

Details Environmentally benign non-toxic fire flooding agents Environmentally benign non-toxic fire flooding agents

2000-07-24

2002-03-05

Anthony, Joseph D. (Department: 1714)

Compositions

Fire-extinguishing

Volatile or gas charged liquids containing

C252S002000, C169S046000, C169S047000

Reexamination Certificate

active

06352648

ABSTRACT:

FIELD OF THE INVENTION
This invention involves novel total flooding and streaming-type fire extinguishants and novel detoxifiers which are environmentally safe and non-toxic in natural form as well as in fire exposed degraded forms.
DESCRIPTION OF THE PRIOR ART
In recent years, it has been discovered that certain halocarbons such as CFC 11, CFC 12, Halon 1301, and the like, which have been widely used as refrigerants, blowing agents and fire extinguishants are damaging to the environment because they accumulate in the stratosphere and damage the integrity of the ozone layer, which protects life on earth from harmful radiation from the sun and space. These harmful substances are being phased out of production.
Halocarbons have been used as fire extinguishants. U.K. 1,603,867, Thacker, discloses CFC 11 and CFC 12 in combination with a monoterpene, that is, an essential oil or citrous oil, as a fire extinguishing agent. A monoterpene is defined in the chemical literature as C
10
H
16
. As stated, CFC 11 and CFC 12 are now well known to be detrimental to the ozone layer.
Halocarbon extinguishants fall into two broad groups, streaming agents and flooding agents. A streaming agent is directed at the source of the fire and should be high boiling to thereby resist decomposition until it reaches the source of the fire. A flooding agent fills a volume around the fire and smothers the fire. It should be low-boiling so that it vaporizes readily.
U.S. Pat. No. 4,826,610, issued May 2, 1989, Derek A. Thacker, discloses a firefighting composition comprising one or more halocarbons, namely Halons 11 (CFC 11), 12 (CFC 12), 113 (CFC 113) and 114 (CFC 114), together with 1% to 14% by weight of the extinguishant base of a sesquiterpene and one or more essential oils. A sesquiterpene is a compound having the formula C
15
H
24
. Solvents and dispersing agents may also be provided. This composition is suited for stream-type firefighting situations. The formulation is not touted to be ozone friendly.
U.S. Pat. No. 4,954,271, issued Sep. 4, 1990, Raymond W. Green, discloses and protects high boiling environmentally amicable stream-type fire extinguishing agents. The stream-type agents comprise in combination: (a) more than 50% by weight of a fluorochlorocarbon selected from the group consisting of: 1,1dichloro-2,2,2-trifluoroethane, and 1,2-dichloro-2,2difluoroethane; (b) less than 48%. by weight of a fluorocarbon selected from the group consisting of: . chlorodifluoromethane, 1-chloro-1,2,2,2-tetrafluoroethane, pentafluoroethane, 1,2,2,2-tetrafluoroethane; and (c) a detoxifying substance selected from the group consisting of terpenes: citral, citronellal, citronellol, limonene, dipentene, menthol, terpinene, terpinolene, sylvestrene, sabinene, methadiene, zingiberene, ocimene, myrcene, &agr;-pinene, &bgr;-pinene, turpentine, camphor, phytol, vitamin A, abietic acid, squalene, lanosterol, saponin, oleanolic acid, lycopene, &bgr;-carotene, lutein, &agr;-terpineol, and p-cymeme; and unsaturated oils; oleic acid, linoleic acid, linolenic acid, eleosearic acid, lincanic acid, ricinoleic acid, palmitoleic acid, petroselenic acid, vaccenic acid, and erucic acid, in the range of from 2 to 10% by weight.
In the chlorofluorocarbon stream-type mixtures taught by Green, it is emphasized that high boiling chlorofluorocarbons should comprise more than 50% weight of his mixtures. In contrast, low boiling compounds must be less than 50% weight (see column 2, lines 22-27). In the examples disclosed in Green, a low boiling chlorofluorocarbon such as CFC 12, which boils at −30° C., amounts to 15% weight of the total formulation. The other components are in the vast majority and boil at temperatures well above 0° C. For instance, in Example 2 of Green, column 4, line 61, the boiling point of the NAF Interior Mixture is stated as being 10° C. Thus, the high boiling mixtures disclosed by Green are useful as stream-type extinguishants and are virtually the opposite of the low boiling mixtures which are suitable as flooding agents.
Two U.S. patents, U.S. Pat. No. 5,141,654, issued Aug. 25, 1992, Fernandez, and U.S. Pat. No. 5,393,438, issued Feb. 28, 1995, Fernandez, are of general interest because they disclose extinguishants. Both patents of Fernandez disclose chlorofluorocarbons which are not fully halogenated, with the provision that there be at least one fluorine atom (see column 2, line 57, of U.S. Pat. No. 5,141,654) in each halocarbon. However, the halocarbons are used in pure form. There is no disclosure in either Fernandez patent of using one or more detoxifying substances. Furthermore, neither Fernandez patent discloses any significance inherent with low boiling chlorofluorocarbons.
SUMMARY OF THE INVENTION
The invention pertains to a fire extinguishing mixture of the formula:
(a). about 90% to 100.0% wt. of a halocarbon selected from the group consisting of:
hydrochlorofluorocarbon.21—dichlorofluoromethane
hydrochlorofluorocarbon.22—chlorodifluoromethane
hydrofluorocarbon 23—trifluoromethane
hydrochlorofluorocarbon.123—2,2-dichloro-l,1,1trifluoroethane
hydrochlorofluorocarbon.123a —1,2-dichloro-1,1,2-trifluoroethane
hydrochlorofluorocarbon.124—2-chloro-1,1,1,2-tetrafluoroethane
hydrochlbrofluorocarbon.124a —1-chloro-1,1,2,2-tetrafluoroethane
hydrofluorocarbon 125—pentafluoroethane
hydrochlorofluorocarbon.131—chlorotrifluoroethane
hydrochlorofluorocarbon.132—1,2-dichloro-l,1-difluoroethane
hydrochlorofluorocarbon.133—2-chloro-1,1,1-trifluorethane
hydrofluorocarbon.134a —1,1,1,2-tetrafluoroethane
hydrofluorocarbon.227—heptafluoropropane
hydrofluorocarbon.236—hexafluoropropane
hydrofluorocarbon.245—pentafluoropropane; and
(b) between 0.25 and 10% by weight of a detoxifying substance selected from the group consisting of all isomers of:
ethene
propene
butene
isoprene
pentene
isopentene
trimethyl ethene
tetramethyl ethene
butadiene
pentadiene
isobutylene
dimethyl butadiene
hexene
hexadiene
methyl pentadiene
hexatriene
the mixture having a boiling point of between about −85° or −80° C. and about −10° C. to 25° C., a formula molecular weight in the range of about 70 to 250, and a vapour pressure of about 0.1 MPa to about 5 MPa at 25° C., said fire extinguishing agent being non-toxic and environmentally benign in both natural form and degraded fire exposed form.
In another aspect, the invention pertains to an additive for halogenated fire extinguishants and fire extinguishing flooding mixtures consisting of one or more hydrocarbons having from two to six carbon atoms, with one or more double bonds, said additive reducing the amount of hydrogen halides and carbonyl halides that are produced on exposure of the extinguishant or mixtures to fire. The additive for halogenated fire extinguishants and fire extinguishing mixtures can have four or more carbon atoms with two or more double bonds, where at least two of the double bonds are conjugated.
The additive can be selected from the group consisting of all isomers of:
ethene
propene
butene
isoprene
pentene
isopentene
trimethyl ethene
tetramethyl ethene
butadiene
pentadiene
isobutylene
dimethyl butadiene
hexene
hexadiene
methyl pentadiene
hexatriene
The invention is also directed to specific additives for halogenated fire extinguishants and fire extinguishing mixtures both for streaming and total flood use consisting of 1,3-butadiene and of isoprene, said additive reducing the amount of hydrogen halides and carbonyl halides that are produced by the halogenated fire extinguishants and fire extinguishing mixtures on exposure to fire. The fluid viscosity of the mixture can be below 1.0 centipoise between the initial boiling point of the mixture and 25° C.
The invention is also directed to a non-toxic environmentally benign fire extinguishing mixture for use in a flooding fire extinguishing technique, said fire extinguishing mixture comprising about 82% by weight HCFC22, about 9.5% by weight HCFC-124, about 4.75% by weight HCFC-123 and about 2% by weight 1,3-butadiene.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
The inventors have deter

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