WO1992008520A1 - Procede et composition pour l'extinction d'incendies - Google Patents

Procede et composition pour l'extinction d'incendies Download PDF

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Publication number
WO1992008520A1
WO1992008520A1 PCT/US1990/006692 US9006692W WO9208520A1 WO 1992008520 A1 WO1992008520 A1 WO 1992008520A1 US 9006692 W US9006692 W US 9006692W WO 9208520 A1 WO9208520 A1 WO 9208520A1
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WO
WIPO (PCT)
Prior art keywords
chloro
pentafluoropropane
hexafluoropropane
dichloro
tetrafluoroethane
Prior art date
Application number
PCT/US1990/006692
Other languages
English (en)
Inventor
Richard Edward Fernandez
Original Assignee
E.I. Du Pont De Nemours And Company
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=32961126&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1992008520(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to ES91901121T priority Critical patent/ES2090301T3/es
Priority to CA002095640A priority patent/CA2095640C/fr
Priority to DE69028119T priority patent/DE69028119T2/de
Priority to JP50148091A priority patent/JP3558630B2/ja
Priority to EP91901121A priority patent/EP0557275B1/fr
Priority to PCT/US1990/006692 priority patent/WO1992008520A1/fr
Publication of WO1992008520A1 publication Critical patent/WO1992008520A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/0057—Polyhaloalkanes

Definitions

  • This invention relates to compositions for use in preventing and extinguishing fires based on the combustion of combustible materials. More particularly, it relates to such compositions that are highly effective and "environmentally safe”. Specifically, the compositions of this invention have little or no effect on the ozone layer depletion process; and make no or very little contribution to th global warming process known as the "greenhouse effect”. Although these compositions have minimal effect in these areas, they are extremely effective in preventing and extinguishing fires, particularly fires in enclosed spaces.
  • halogenated hydrocarbon fire extinguishing agents are currently preferred. These halogenated hydrocarbon fire extinguishing agents are not only effective for such fires, but also cause little, if any, damage to the room or its contents. This contrasts to the well-known "water damage” that can sometimes exceed the fire damage when the customary water pouring process is used.
  • the halogenated hydrocarbon fire extinguishing agents that are currently most popular are the bromine-containing halocarbons, e.g. bromotrifluoromethane (CF-Br, Halon 1301) and bromochlorodifluoromethane (CF.ClBr, Halon 1211) . It is believed that these bromine-containing fire extinguishing agents are highly effective in extinguishing fires in progress because, at the elevated temperatures involved in the combustion, thes compounds decompose to form products containing bromin atoms which effectively interfere with the self-sustaining free radical combustion process and, thereby, extinguish the fire.
  • These bromine-containin halocarbons may be dispensed from portable equipment o from an automatic room flooding system activated by a fire detector.
  • fires may occur in rooms, vaults, enclosed machines, ovens, containers, storage tanks, bins and like areas.
  • Patent 3,715,4308 discloses creating an atmosphere in a fixed enclosure which does not sustain combustion. Huggett provides an atmosphere consisting essentially of air, a perfluorocarbon selected from carbon tetrafluoride, hexafluoroethane, octafluoropropane and mixtures thereof.
  • bromine- containing halocarbons such as Halon 1211 can be used to provide an atmosphere that will not support combustion.
  • the high cost due to bromine content and the toxicity to humans i.e. cardiac sensitization at relatively low levels make the bromine-containin materials unattractive for long term use.
  • even more serious objection to the use of brominated halocarbon fire extinguishant has arisen.
  • the depletion of the stratospheric ozone layer, and particularly the role of chlorofluorocarbon (CFC's) have led to great interest in developing alternative refrigerants, solvents, blowing agents, etc.
  • bromine-containing halocarbons such as Halon 1301 and Halon 1211 are at least as active as chlorofluorocarbons in the ozone layer depletion process. While perfluorocarbons such as those suggested by Huggett, cited above, are believed not to have as much effect upon the ozone depletion process a chlorofluorocarbons, their extraordinarily high stability makes them suspect in another environmental area, that of "greenhouse effect". This effect is caused by accumulation of gases that provide a shield against heat transfer and results in the undesirable warming of the earth's surface.
  • the present invention is based on the findi that an effective amount of a composition comprising least one partially fluoro-substituted ethane selecte from the group of pentafluoroethane (CF.-CHF-) , also known as HFC-125, the tetrafluoroethanes (CHF--CHF- a CF 3 -CH 2 F) , also known as HFC-134 and HFC-134a, the chlorotetrafluoroethanes (CF 3 -CFHC1 and CF 2 C1-CF H) , also known as HCFC-124 and HCFC-124a, the dichlorotrifl ⁇ oroethanes (CF 3 -CHC1 2 and CF 2 C1-CHFC1) , also known as HCFC-123 and HCFC-123a, and the di ⁇ hlorodifluoroethanes (CHFCl-CHFCl and CC1 F-CH 2 F) , also known
  • the preferred group comprises CF 3 -CHF 2 , CF 3 -CH 2 F and CF 3 -CHC1 2 .
  • the partially fluoro-substituted ethanes above may be used in conjunction with as little as 1% of at least one halogenated hydrocarbon selected from the group of difluoro ethane (HFC-32) , chlorodifluoromethane (HCFC-22) , 2,2-dichloro-l,l,l-trifluoroethane (HCFC-123) , l,2-dichloro-l,l,2-trifluoroethane (HCFC-123a) , 2-chloro-l,1,1,2-tetrafluoroethane (HCFC-124) , 1-chloro-l,1,2,2-tetrafluoroethane (HCFC-124a) , pentafluoroethane (HFC-125) , 1,1,2,2-tetrafluoroethane (HFC-
  • the partially fluoro-substituted ethanes when added in adequate amounts to the air in a confine space, eliminates the combustion-sustaining properties of the air and suppresses the combustion of flammable materials, such as paper, cloth, wood, flammable liquids, and plastic items, which may be present in th enclosed compartment.
  • fluoroethanes are extremely stable and chemically inert. They do not decompose at temperatures as high as 350 ⁇ C to produce corrosive or toxic products and cannot be ignited even in pure oxygen so that they continue to be effective as a flam suppressant at the ignition temperatures of the combustible items present in the compartment.
  • the particularly preferred fluoroethanes are extremely stable and chemically inert. They do not decompose at temperatures as high as 350 ⁇ C to produce corrosive or toxic products and cannot be ignited even in pure oxygen so that they continue to be effective as a flam suppressant at the ignition temperatures of the combustible items present in the compartment.
  • the particularly preferred fluoroethanes are extremely stable and chemically inert. They do not decompose at temperatures as high as 350 ⁇ C to produce corrosive or toxic products and cannot be ignited even in pure oxygen so that they continue to be effective as a flam suppressant at the ignition temperatures of the combustible items present in the
  • HFC-125, HFC-134, and HFC-134a, as well as HCFC-124 ar additionally advantageous because of their low boiling points, i.e. boiling points at normal atmospheric pressure of less than -12 # C.
  • these gases will not liquefy and will not, thereby, diminish the fire preventive properties of the modifie air.
  • any material having such a low boiling point would be suitable as a refrigerant.
  • the fluoroethane HFC-125 is also characterized by an extremely low boiling point and high vapor pressure, i.e. above 164 psig at 21'C. Thi permits HFC-125 to act as its own propellant in "hand-held" fire extinguishers.
  • Pentafluoroethane may also be used with other materials such a those disclosed on pages 5 and 6 of this specificatio to act as the propellant and co-extinguishant for the materials of lower vapor pressure.
  • these other materials of lower vapor pressure may be propelled from a portable fire extinguisher by the usual propellants, i.e. nitrogen or carbon dioxide.
  • propellants i.e. nitrogen or carbon dioxide.
  • the gas or gases should be added in an amount which will impart to the modified air a heat capacity per mole of total oxygen present sufficient to suppress o prevent combustion of the flammable, non-self-sustaining materials present in the enclosed environment.
  • the minimum heat capacity required to suppress combustion varies with the combustibility of the particular flammable materials present in the confined space. It is well known that the combustibility of materials, namely their capability for igniting and maintaining sustained combustion under a given set of environmental conditions, varies according to chemical composition and certain physica properties, such as surface area relative to volume, heat capacity, porosity, and the like. Thus, thin, porous paper such as tissue paper is considerably mor combustible than a block of wood.
  • a heat capacity of about 40 cal./ ⁇ C and constant pressure per mole of oxygen is more than adequate to prevent or suppress the combustion of materials of relatively moderate combustibility, such as wood and plastics.
  • a minimum heat capacity of 45 cal./"C per mole of oxygen is generally adequate for moderately combustible materials and a minimum of about 50 cal./ ⁇ C per mole of oxygen for highly flammable materials.
  • Heat capacity per mole of total oxygen can be determined by the formula:
  • the air in the compartment can be treated at any time that it appears desirable.
  • the modified air can be used continuously if a threat of fire is constantly present or if the particular environment is such that the fire hazard must be kept at an absolute minimum; or the modified air can be used as an emergency measure if a threat of fire develops.
  • the fire extinguishing agent is added to the air stream prior to its entry into the glass bead distributor while the air flow rate is maintained at 40 liters/minute for all tests.
  • the air and agent flow rates are measured using calibrated rotameters. Each test is conducted by adjusting the fuel level in the reservoir to bring the liquid fuel level in the cup burner just even with the ground glass lip on the burner cup. With the air flow rate maintained at 40 liters/minute, the fuel in the cup burner is ignited.
  • the fire extinguishing agent is added in measured increments until the flame is extinguished.
  • the fire extinguishing concentration is determined fro the following equation:
  • F. Agent flow rate
  • F. Air flow rate
  • the cardiac sensitivity is measured using unanesthesized, healthy dogs using the general protocal set forth in the Reinhardt et al article.
  • the dog is subjected to air flow through a semiclosed inhalation system connected to a cylindrical face mask on the dog.
  • epinephrine hydrochloride adrenaline
  • saline solution diluted with saline solution
  • air containing various concentrations of the agent being tested is administered followed by a second injection of epinephrine.
  • concentrations of agent necessary to produce a disturbance in the normal conduction of an electrical impulse through the heart as characterized by a serious cardiac arrhythmia are shown in the following table.
  • ODP ozone depletion potential
  • the ODP is the ratio of the calculated ozone depletion in the stratosphere resulting from the emission of a particular agent compared to the ODP resulting from the same rate of emission of FC-11 (CFC13) which is set at 1.0.
  • Ozone depletion is believed to be due to the migration of compounds containing chlorine or bromine through the troposphere into the stratosphere where these compounds are photolyzed by UV radiation into chlorine or bromine atoms.
  • the ozone depletion potential is also discussed in "Ultraviolet Absorption Cross-Sections of Several Brominated Methanes and Ethanes" L. T. Molina, M. J. Molina and F. S. Rowland” J. Phys. Chem. 86, 2672-2676 (1982); in Bivens et al. U.S. Patent 4,810,403; and in "Scientific Assessment of Stratospheric Ozone: 1989" U.N. Environment Programme (21 August 1989) .
  • the ozone depletion potentials are presented for the fluoroethanes used in this invention and various controls.
  • the GWP also known as the "greenhouse effect” is a phenomenon that occurs in the troposphere. It is calculated using a model that incorporates parameters based on the agent's atmospheric lifetime and its infra-red cross-section or its infra-red absorption strength per mole as measured with an infra-red spectrophotometer.

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  • 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)

Abstract

Procédé servant à éteindre, prévenir et lutter contre les incendies en utilisant une composition contenant au moins un éthane fluoro-substitué choisi dans le groupe comprenant CF3-CHF2, CHF2-CHF2, CF3-CH2F, CF3-CHFCl, CF2-Cl-CHF2, CF3-CHCl2, CF2Cl-CHFCl, CFCl2-CHF2, and CHFCl-CHFCl. Lesdits éthanes peuvent être utilisés dans des zones ouvertes ou fermées et ont un effet négligeable ou nul sur l'ozone de la stratosphère et peu d'effet sur le processus de réchauffement général de la planète.
PCT/US1990/006692 1990-11-15 1990-11-15 Procede et composition pour l'extinction d'incendies WO1992008520A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES91901121T ES2090301T3 (es) 1990-11-15 1990-11-15 Procedimiento para la extincion de incendios.
CA002095640A CA2095640C (fr) 1990-11-15 1990-11-15 Composition servant a eteindre un incendie et methode de production de cette composition
DE69028119T DE69028119T2 (de) 1990-11-15 1990-11-15 Feuerlöschverfahren
JP50148091A JP3558630B2 (ja) 1990-11-15 1990-11-15 防火方法および防火組成物
EP91901121A EP0557275B1 (fr) 1990-11-15 1990-11-15 Procede pour l'extinction d'incendies
PCT/US1990/006692 WO1992008520A1 (fr) 1990-11-15 1990-11-15 Procede et composition pour l'extinction d'incendies

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1990/006692 WO1992008520A1 (fr) 1990-11-15 1990-11-15 Procede et composition pour l'extinction d'incendies

Publications (1)

Publication Number Publication Date
WO1992008520A1 true WO1992008520A1 (fr) 1992-05-29

Family

ID=32961126

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/006692 WO1992008520A1 (fr) 1990-11-15 1990-11-15 Procede et composition pour l'extinction d'incendies

Country Status (6)

Country Link
EP (1) EP0557275B1 (fr)
JP (1) JP3558630B2 (fr)
CA (1) CA2095640C (fr)
DE (1) DE69028119T2 (fr)
ES (1) ES2090301T3 (fr)
WO (1) WO1992008520A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592019A1 (fr) * 1989-10-04 1994-04-13 E.I. Du Pont De Nemours And Company Composition et procédé pour éteindre des incendies
KR101186225B1 (ko) * 2002-08-29 2012-09-28 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 마그네슘 및 마그네슘 합금의 트윈 롤 캐스팅
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2594319B1 (fr) 2011-11-18 2018-05-30 Minimax GmbH & Co KG Installation d'extinction ou d'intertisation à l'aide d'un agent d'extinction liquide synthétique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3479286A (en) * 1965-09-22 1969-11-18 Montedison Spa Flame-extinguishing compositions
US3656553A (en) * 1969-05-16 1972-04-18 Montedison Spa Flame-extinguishing substance comprising 1,2-dibromohexafluropropane
US3844354A (en) * 1973-07-11 1974-10-29 Dow Chemical Co Halogenated fire extinguishing agent for total flooding system
US4459213A (en) * 1982-12-30 1984-07-10 Secom Co., Ltd. Fire-extinguisher composition
US4954271A (en) * 1988-10-06 1990-09-04 Tag Investments, Inc. Non-toxic fire extinguishant

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1926395A (en) * 1930-07-31 1933-09-12 Frigidaire Corp Process of preventing fire by nontoxic substances

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3479286A (en) * 1965-09-22 1969-11-18 Montedison Spa Flame-extinguishing compositions
US3656553A (en) * 1969-05-16 1972-04-18 Montedison Spa Flame-extinguishing substance comprising 1,2-dibromohexafluropropane
US3844354A (en) * 1973-07-11 1974-10-29 Dow Chemical Co Halogenated fire extinguishing agent for total flooding system
US4459213A (en) * 1982-12-30 1984-07-10 Secom Co., Ltd. Fire-extinguisher composition
US4954271A (en) * 1988-10-06 1990-09-04 Tag Investments, Inc. Non-toxic fire extinguishant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0557275A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0592019A1 (fr) * 1989-10-04 1994-04-13 E.I. Du Pont De Nemours And Company Composition et procédé pour éteindre des incendies
KR101186225B1 (ko) * 2002-08-29 2012-09-28 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 마그네슘 및 마그네슘 합금의 트윈 롤 캐스팅
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition

Also Published As

Publication number Publication date
DE69028119T2 (de) 1997-02-20
EP0557275B1 (fr) 1996-08-14
JPH06501628A (ja) 1994-02-24
JP3558630B2 (ja) 2004-08-25
EP0557275A4 (en) 1993-09-29
CA2095640C (fr) 2004-10-19
CA2095640A1 (fr) 1992-05-16
DE69028119D1 (de) 1996-09-19
EP0557275A1 (fr) 1993-09-01
ES2090301T3 (es) 1996-10-16

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