WO1996034661A1

WO1996034661A1 - Method for the suppression of hydrogen fires

Info

Publication number: WO1996034661A1
Application number: PCT/US1996/006045
Authority: WO
Inventors: Mark L. Robin; Charles J. Mazac; John S. Rubacha
Original assignee: Great Lakes Chemical Corporation
Priority date: 1995-05-03
Filing date: 1996-05-01
Publication date: 1996-11-07

Abstract

A method for extinguishing hydrogen fires comprises introducing to the hydrogen fire a fire extinguishing concentration of 1,1,1,2,3,3,3-heptafluoropropane and maintaining the concentration until the fire is extinguished. The method includes heptafluoropropane at a range of 13-30 % volume/volume in the air. The fire extinguishing methods also include the use of heptafluoropropane in blend with other fire extinguishing compounds.

Description

METHOD FOR THE SUPPRESSION OF HYDROGEN FIRES

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

The present invention relates to the protection of hydrogen-containing hazards and the suppression of hydrogen combustion and fires.

DESCRIPTION OF THE PRIOR ART

The use of certain bromine-containing 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 for flame suppression is the radical trap mechanism proposed by Fryburg in "Review of Literature Pertinent to Fire Extinguishing Agents and to Basic Mechanisms Involved in Their Action",

NACA-TN 2102 (1950). It is generally accepted that compounds containing the halogens chlorine, bromine and iodine act by interfering with free radical or ionic species in the flame; the presence of fluorine had not been considered as contributing to the fire extinguishing properties of a compound, but will impart stability, reduce toxicity and boiling point and increase thermal stability.

Various halogenated hydrocarbons have been employed as fire extinguishants . Prior to 1945, three halogenated extinguish] ng agents widely used were carbon tetrac lo ide, methyl bromide and bromochloromethane. For toxicological reasons, however, the use of these agents has been discontinued. The three fire extinguishing compounds presently in common use are bromine-containing compounds, Halon 1301 (CF Br) , Halon 1211 (CF₂BrCl) and Halon 2402 (BrCF CF_Br) . The effectiveness of these three volatile bromine-containing compounds in extinguishing fires has been described in United States Patent No. 4,014,799, issued to Owens. The National Fire Protection Association (NFPA) publication, The Fire Protection Handbook, Section 18, Chapter 2, entitled "Halogenated Agents and Systems" (1985) describes these agents in more detail.

Although the above-named bromine-containing compounds are effective fire fighting agents, those agents containing bromine or chlorine are asserted to be capable of the destruction of the earth's protective ozone layer. For example, Halon 1301 has an Ozone Depletion Potential (ODP) rating of 10, and Halon 1211 has an ODP of 3. As a result of concerns over ozone depletion, the production and sale of these agents after January 1, 1994 is prohibited under international and United States policy. It is therefore an object of this invention to provide a method for extinguishing fires as rapidly and effectively as the techniques using presently employed Halons while avoiding the above-named drawbacks.

Hydrogen is an important industrial chemical in petroleum refining, in the synthesis of methanol and ammonia, and in the manufacture of various chemicals. Hydrogen also finds use in metallurgical processing, vegetable-oil hydrogenation, electronics manufacture and fuel cell applications (Kirk-Othmer Encyclopedia of Chemical Technology, 5th ed., volume 13). The danger in the use of hydrogen lies in its extreme flammability in oxygen or air. Hydrogen is odorless, colorless, and burns with an almost invisible flame. As a result, hydrogen is not readily detected, further increasing the danger of its use compared to other flammable substances. Detonation and flammability limits for hydrogen are wider than those of most other flammable gases.

The difficulty of suppressing hydrogen combustion and fires is evident from the large quantities of Halons, in particular Halon 1301, required for suppression. Whereas a large selection of Class A and Class B fuels are sufficiently protected by a concentration of 5 percent by volume Halon 1301, suppression of hydrogen fires with Halon 1301 requires at least 20 percent by volume Halon 1301 (C.E. Ford, Halon 1301 Fire-Extinguishing Agent: Properties and Applica ions, in Fire Protection by Halons, NFPA, 1975.).

It is a further object of this invention to provide an agent for use in a method for the suppression of hydrogen combustion that is efficient, economical and environmentally safe with regard to ozone depletion.

-A -

SUMMARY OF THE INVENTION

Briefly describing one aspect of the present invention there is provided a method of extinguishing hydrogen fires that comprises introducing to the fire a fire extinguishing concentration of an extinguishant composition including 1,1,1,2,3,3,3-Heptafluoroρropane (HFC-227ea, CF CHFCF ) , and maintaining the concentration of the composition until the fire is extinguished. 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane may be used alone, or in combination with other fire extinguishants . Blends of 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane with other such extinguishants are also contemplated for use.

It is an object of the present invention to provide an effective method for extinguishing hydrogen fires which employs compounds that are environmentally safe, and which have low ozone depletion potential and greenhouse warming effect. A further object of the present invention is to provide fire extinguishing methods for hydrogen fires using compositions comprising blends of 1, 1, 1, 2, 3, 3 , 3-heptafluoropropane and other extinguishing agents, which blends are effective and safe in use. A further object of the present invention is the protection of hydrogen containing hazards with 1,1,1,2,3,3,3- heptafluoropropane. Examples of such hazards include, but are not limited to, petroleum refineries, ammonia synthesis plants, methanol production facilities, cyclohexane, benzene, oxo alcohol and aniline production facilities, metallurgical processing facilities, reduced gas blanketing processes, edible fats and oils production facilities, float glass manufacturing, electronics industry applications, fuel cells, electrolytic cells, hydrogen powered vehicles, and cryogenic and corrosion prevention applications.

Further objects of the present invention will be apparent from the description which follows. BRIEF DESCRIPTION OF THE DRAWING

FIG.l is a diagrammatic view of a cup burner test system used in demonstrating the novel aspects of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For the purpose of promoting an understanding of the principles of the invention, reference will now be made to preferred embodiments of the invention and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations, further modifications and applications of the principles of the invention as described herein being contemplated as would normally occur to one skilled in the art Lo which the invention relates. In accordance with the present invention, 1, 1, 1,2, 3,3, 3-heptafluoropropane (CF CHFCF ) has been found to be an effective extinguishant for hydrogen fires. However, because 1, 1, 1,2, 3 , 3 , 3-heρtafluoropropane contains no bromine or chlorine, it has an ozone depletion potential of zero. In one aspect, the invention relates to methods for extinguishing hydrogen fires which are improved by using 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane alone, or in a blend, as the fire extinguishing agent. 1, 1, 1,2,3,3, 3-Heptafluoropropane (CF CHFCF ) is a halogenated hydrocarbon with a molecular weight of 170 and a boiling point of -16°C. It has been employed as a fire suppression agent for various class fuels, as described in U.S. Patent 5,124,053. However, because 1,1,1,2,3,3,3- heptafluoropropane lacks a bromine atom, it is generally recognized as a much less efficient fire supppression agent compared to Halon 1301, on both a volume and weight basis. For example, the extinguishment of n-heptane diffusion ilαine:; requires 3 percent by volume Halon 1301, and 6 percent 1, 1, 1,2, 3,3, 3-heptafluoropropane (NFPA 2001 Standard on Clean Agent Fire Extinguishing Systems, NFPA, 1994 edition). Surprisingly, we have found that 1,1,1,2,3,3,3- heptafluoropropane is uniquely superior to Halon 1301 in the suppression of hydrogen fires, on both a volume and weight basis. In accordance with one embodiment of the present invention, there is provided a method for extinguishing hydrogen fires which includes the use of

1, 1, 1, 2 , 3 , 3 ,3-hepta luoropropane as a fire extinguishing aqent. In use with hydrogen fires,

1, 1, 1, 2 , 3,3 , 3-heptafluoropropane may be applied in the variety of methods employed for other halogenated hydrocarbons, including application in a flooding system, portable system or specialized system. 1, 1, 1, 2 , 3 , 3 , 3-Heptafluoropropane is effective in lower concentrations than Halon 1301, and of course at higher concentrations as well. The concentration employed may depend to some extent on the circumstances of applica ion. Generally, application rates of 1, 1, 1,2 ,3 ,3 ,3-heptafluoropropane alone preferably range from at least about 13%, and more preferably between about 15% and 30% v/v.

A further desirable aspect of the present invention is that 1, 1, 1, 2 , 3 ,3 , 3-heptafluoropropane is environmentally safer than many of the prior art halogenated hydrocarbon fire extinguishing agents. 1, 1, 1, 2 , 3 , 3 , 3-Heptafluoropropane has an ODP of zero, compared to an ODP of 10 for Halon 1301 and of 3 for Halon 1211, two common commercial fire extinguishants . It is also an aspect of the present invention that

1, 1, 1, 2 , 3, 3 , 3-heptafluoropropane may be employed in use with hydrogen fires with other extinguishants. The resulting blend will have improved characteristics in terms of efficacy, toxicity and/or environmental safety depending on the blend and the application. Among the other agents with which 1, 1, 1, 2 , 3, 3 , 3-heptafluoropropane may be blended are iodine, chlorine and/or bromine containing compounds such as iodotrifluoromethane (CF.,1), Halon 1301 (CF-.Br), Ilalon 1211 (CF₂BrCl), Ilalon 2402 (BrCF₂CF₂Br) , Halon 1201 (CF IIBr) and 2-chloro-l, 1, 1, 2-tetrafluoroethane (CF„CHFC1), and hydiofluorocaibons such as trifluoromethane (CF H), pentafluoroethane (CF CF i), 1,1,1,3,3, 3-hexafluoropropane (CF CH CF , 1,1, 1,2,3,3-hexafluoropropane (CF₃CHFCF₂H) , 1, 1,2, 2,3, 3-hexafluoropropane (HCF CF CF H) , and

1, 1, 1,2, 2,3, 3-heptafluoropropane (CF₃CF₂CF₂H) . Wheie 1, 1, 1,2 ,3 ,3 ,3-heptafluoropropane of this invention is employed in a blend, 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane may be combined, preferably in an amount of from about 1% to about 99% by weight of the blend, with one or more of these compounds. Mixtures of 1, 1 , 1, 2 , 3 , 3 , 3-heptafluoropropane with the hydrofluorocarbons are especially preferred because said mixtures have an ODP of zero.

The relative amounts of the 1,1,1,2,3,3,3- heptafluoropropane and other compounds is not critical, but rather is dictated by the characteristics desired for the overall composition. Thus, in certain applications there may be a greater need for low toxicity, and in other instances, the emphasis may be on high efficacy. Therefore, no particular ratios of compounds are required.

The methods for application of the described fire extinguishing compositions are those known to be useful foi the Halon agents. In broad terms, these methods utilize application systems which typically include a supply of agent, a means for releasing or propelling the agent from its container, and one or more discharge nozzles to apply the agent into the hazard or directly onto the burning object. Thus, the agents of this invention may be used in total flooding systems in which the agent in introduced into an enclosed region surrounding a fire at a concentration sufficient to extinguish the fire. In accordance with a total flooding system, equipment or even rooms may be provided with a source of agent and appropriate piping, valves and controls so as to automatically and/or manually 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 500 psig at ambient conditions, and stored in the system as the superpressurized agent. Alternatively, the fire extinguishant may be pressurized with nitrogen or other inert gas at the time of system activation.

Alternatively, the compositions of the invention 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 gases in order to ensure that the agent is completely expelled from the extinguisher.

1, 1, 1, 2 , 3 , 3 , 3-Heρtafluoropropane containing systems in accordance with this invention may be conveniently pressurized at any desirable pressure up to about 600 psig at ambient conditions, ether prior to or at the time of system activation.

The invention will be further described with reference to the following specific Examples. However, it will be understood that these Examples are illustrative and not restrictive in nature.

EXAMPLE 1

Dynamic extinguishment test data for 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane were obtained employing the cup burner test procedure in which air and the agent are continuously supplied to a hydrogen flame produced in a glass cup burner (see Figure 1). The apparatus includes a cup 10 having a height 11 of 610mm and a diameter 12 of 102mm. Fuel from the reservoir 13 to a burner 14 having a diameter of 28mm and a height above the top of the mixing chamber 15 of 178mm. The mixing chamber 15 is 102mm high and includes beads 16 stacked to a height of 76mm. Air and fire extinguishant are fed in with rotameters 17 and 18 and lines 19 and 20. In this manner, the air and extinguishant are mixed and diffuse upwardly from the chamber 15 to the flame at the top of the burner 14. The cup burner apparatus is commonly employed for the evaluation of the relative effectiveness of fire suppression agents, and has been described for example in NFPA 2001 Standard on Clean Agent Fire Extinguishing Systems , 1 9 edition. Vapor of the agent to be tested is mixed with air and introduced to the flame, with the concentration of agent in air being increased slowly until the flow is just sufficient to cause extinction of the flame. Data were obtained in this fashion for 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane and for comparative purposes, for Halon 1301. The percent of each agent in air (v/v) required to extinguish hydrogen flames is given in Table 1.

This example demonstrates the superior performance of 1 , 1, 1,2 , 3, 3 ,3-heptafluoropropane compared to Halon 1301 for the suppression of hydrogen combustion.

EXAMPLE 2

Dynamic extinguishment data were obtained for the extinguishment of diffusion flames of a number of fuels as described in Example 1 for 1, 1, 1, 2, 3 , 3 , 3-heptafluoropropane and Halon 1301, and the results are also shown in Table 1. This example demonstrates the usually encountered superior perfor ance of Halon 1301 on Class B fuels compared to 1, 1, 1, 2 , 3 , 3 , 3-heptafluoropropane . By comparison, it is shown that 1, 1, 1,2 ,3 ,3 , 3-heptafluoropropane has unique and surprising superior efficacy when used with hydrogen fires. Table 1 .

Ext. Concentration, , % v/v

Fuel CF3CHFCF3 HaJ Lon 1301

Hydt ogen 13.2 18.3 Acetone 6.9 3.3

AV gas 6.5 3.3

Diesel 6.7 2.1

Diethyl Ether 7.5 3.7

Ethane 6.7 4.4 Ethanol 8.3 3.8

Ethylene 8.4 6.3

Methane 5.5 2.5

Methanol 10.4 7.2

Methyl Ethyl Ketone 7.4 3.5 Propane 6.7 3. b

EXAMPLE 3

1, 1 , 1, 2 , 3 , 3 , 3-Heptafluoropropane is used at varying concentrations for extinguishment of hydrogen fire. Repeating for example, the test procedure of Example 1, v/v concentrations of heptafluoropropane in the air suirounding a hydrogen fire include 13%, 15%, 20%, 25% and 30% and are effective in extinguishing the hydrogen fire.

EXAMPLE 4

Repeating the foregoing examples with respect to lieptafluoropropane, except using blends of heptafluoropropane with other fire extinguishants, yields similar results. The blends include the compounds previously identified. Depending on the blend mixtures, concentrations of the overall blend at 10%, 20% and 30% v/v are effective in extinguishing the hydrogen fire. The blends include those compounds previously indicated, for example,

1, 1, 1, 2 , 3 , 3 , 3-heptafluoroproane and one or more compounds selected from the group CF_I, CF_Br, CF BrCl,

BrCF₂CF₂Br, CF₂HBr, CF₃CHFCi, CF..H, CF₃CF₂H,

CF₃CH₂CF₃, CF₃CHFCF₂II, HCF₂CF₂CF₂H, and

CF CF_CF₂H. The blend compositions include ranges from

1% to 99% 1, 1, 1,2 ,3 ,3 ,3-heptafluoropropane, and are effective in use with hydrogen fires.

Claims

WHAT IS CLAIMED IS:

1. A method for extinguishing a hydrogen fire comprising the steps of: a. introducing to the fire a fire extinguishing concentration of a composition consisting essentially of

1,1,1,2,3,3, 3-heptafluoropropane; and b. maintaining the concentration of the composition until the fire is extinguished.

2. The process of claim 1 wherein the composition is employed at a level of less than about 30% v/v in the air.

3. The process of claim 2 wherein the extinguishing concentration of the composition is from about 13% to 25% v/v in the air.

4. The process of claim 1 wherein the composition is employed in a total flooding system.

5. The process of claim 1 wherein the composition is employed in a portable extinguishing system.

6. The process of claim 1 wherein the composition is superpressurized with an inert gas prior to step a.

7. The process of claim 1 wherein the composition is superpressurized with an inert gas at the time of step a.

8. A method for extinguishing a hydrogen fire comprising the steps of: a. introducing to the fire a fire extinguishing concentration of a mixture comprising: a composition consisting essentially of

1, 1, 1,2 ,3 ,3 ,3-heptafluoroproane and one or more compounds selected from the group consisting of CF_I, CF Br, CF BrCl, BrCF CF Br, CF₂HBr, CF CHFC1, CF H,

CF₃CF₂H, CF₃CH₂CF₃, CF₃CHFCF₂H,

HCF₂CF₂CF₂H, and CF₃CF₂CF₂H where the compound is present in the mixture at a level of between

1% and 99% by weight of the mixture; and b. maintaining the concentration of the mixture until the fire is extinguished.

9. The method of claim 8, wherein the fire extinguishing concentration of the mixture is about 10 to 30% v/v in the air.

10. The process of claim 8 wherein the composition is employed in a total flooding system.

11. The process of claim 8 wherein the composition is employed in a portable extinguishing system.

12. The process of claim 8 wherein the composition is superpressurized with an inert gas prior to step a.

13. The process of claim 8 wherein the composition is superpressurized with an inert gas at the time of step α.