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
  • A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components

Definitions

• the present invention relates to the field of extinguishing a fire, in particular, to a fire extinguishing aerosol forming means (FEAFM) .
• FEM fire extinguishing aerosol forming means
• Fire extinguishing aerosol forming means have presently wide application as an effective volumetric fire extinguishing means because they are characterized by fast emitting of the fire extinguishing aerosol and fast filling the protected volume therewith, entering even into difficult places, in result the fire will be practically instantly liquidated (PCT/RU 93/00025 of Jan. 28,1993, A 62D 1/00; EP 0560095 of Jan. 25,1995, A 62D 1/00).
• Extinguishing a fire with use of FEAFM is based on a principally new mechanism consisting in burning of the means with formation of gaseous and highly dispersed condensed products having inhibiting properties and suppressing the chain reaction of burning and, as result, extinguishing the flame. Aerosol formed at burning of such means has fire extinguishing properties due to the presence of alkaline metals ions therein. Potassium nitrate or a mixture thereof with potassium perchlorate is most frequently used as a source of alkaline metals ions in FEAFM.
• the known FEAFM differ, as a rule, by type of binder and contain of additives of various purpose (Patents RU No.2105581 A 62C 3/00 and No.2091106 A 62D 1/00) .
• fire extinguishing efficiency and aerosol forming speed should be rather high, and temperature of the fire extinguishing aerosol should be low.
• high speed of aerosol forming corresponds to increased temperature of the aerosol, and significant reduction of the aerosol temperature results in loss in fire extinguishing efficiency thereof.
• aerosol forming fire extinguishing composition described in the Patent of the Russian Federation No.2091106, A 62D 1/00, comprising the following components, in mass %: potassium nitrate 45.0 - 75.0; carbon 4.0 -• 11.0; centralyte and/or diphenylamine 0.5 - 2.0; industrial or instrumental oil 0.5 - 2.5; zinc and/or sodium stearate, or mixture thereof with sulforicinate and gelatin 0.02-0.5; burning catalyst and/or inhibitor 0.5 - 20.0; plasticized derivative of cellulose, or mixture thereof with additional binder the rest
• the burning catalyst FEAFM comprises compounds chosen from the sequence including oxides of metals of variable valence or metals of the II group (oxides of iron, copper, nickel, cobalt, manganese, chrome and zinc, or mixture thereof) , their organic or inorganic compositions or mixture thereof (salicylates, phthalates, acetylacetolates or oxalates of copper, nickel, cobalt, iron, manganese, zinc or calcium; carbonates of. these metals, except calcium carbonate).
• the burning inhibitor FEAFM comprises compounds chosen from the sequence including inorganic and organic phosphor containing compounds, inorganic and organic nitrogen containing compounds, hydroxides, carbonates, basic carbonates, borates of metals or trioxide of aluminum and/or mixtures thereof.
• the modern fire extinguishing means based on use of aerosol forming compositions provide, as a rule, presence of various agents ensuring cooling of the fire extinguishing aerosol: cooling liquids (water, water solutions of salts), air ejectors, chemical thermally decomposing powders or compositions.
• compositions for cooling of the fire extinguishing aerosol containing as a binder cellulose nitrate, plasticized by a low-volatile plasticizer, diphenylamine, polyvinyl acetate, carbon, iron oxide, as a filler basic manganese carbonate, or ammonium oxalate, or basic magnesium phosphate; and technological additives: industrial or instrumental oil, sodium or zinc stearate, graphite, paraffin and water at the following contents of the components, mass %: cellulose nitrate 5.0 - 12.5; low-volatile plasticizer 5.0 - 12,5; diphenyl amine 0.1 - 0.5, polyvinyl acetate 0.2 - 1,5, carbon 0.1 - 0.5, iron oxide 0.3 - • 1.5 , basic manganese carbonate of ammonium oxalate or basic magnesium phosphate 25.0 - 45.0; industrial or instrumental oil
• This composition for cooling of aerosol is insufficiently effective because of low contents of the heat absorbing component (25-45 weight %) . Furthermore, rheological, physical and mechanical properties of the composition limit the forms of joint application thereof directly with aerosol forming compositions.
• a fire extinguishing aerosol forming means including flame suppressing agent, fuel-binder, source of carbon, stabilizer, modifier of burning and technological additives, and as the flame suppressing agent it contains nitrates of alkaline metals or mixture thereof with complex compositions of alkaline metals, as the source of carbon - carbon as it or aliphatic or aromatic alcohols, or mixture thereof, as the modifier of burning it additionally contains a cooling agent, and as the technological additives it additionally contains compositions chosen from the class of glycoles or glycerin.
• Main ingredients of the means are contained therein in the following ratio, mass parts: flame suppressing agent 35 - 80, fuel-binder 12 - 40, source of carbon 1 - 15; stabilizer 0.5 - 2,5; modifier of burning 1 - 250; technological additives 0.5 - 7.5.
• Nitrates of alkaline metals or mixture thereof with complex compositions of alkaline metals are used as the flame suppressing agent.
• compositions of alkaline metals comprise compositions having temperature of chemolysis of approximately 200 2 C, that is commensurable with the surface temperature of burning FEAFM.
• these compositions it is preferable to use potassium or sodium dipyrocatechol, potassium hexanitrocobaltate, potassium ferrocyanide or potassium ferricyanide, or mixture thereof.
• Products formed at decomposition of the complexes have superfluous energy and are active accelerators of reactions taking place in the surface layer of FEAFM. This results in increasing of completeness of potassium nitrate decomposition.
• the products of chemolysis of the complex compositions of alkaline metals are also capable to break off the chain reactions of oxidation at burning process and, together with decomposition products of potassium nitrate, form a mixture effectively inhibiting process of burning .
• Plasticized derivatives of cellulose or mixture thereof with other binder is used as a fuel-binder. It is preferred to use such compositions, as cellulose ethers, e.g. nitrocellulose, cellulose methyl-, ethylacetates or mixtures thereof .
• plasticizers of cellulose derivatives there are used ethers of carboxylic or mineral acids and alcohols, e.g., triacetin, diethylene glycol propionate, triethylene glycol dipropionate, dibutyl phthalate, dioctyl sebacate, diethylene glycol dinitrate or triethylene glycol dinitrate or mixture thereof.
• FEAFM can contain polyvinyl acetate, or polyvinyl alcohol, or mixture thereof as an additional binder.
• the means contains carbon as such, aliphatic or aromatic alcohols (e.g., sorbitol, xylitol, pirocathechol, hydroquinone or -naphthol) or mixture thereof .
• aliphatic or aromatic alcohols e.g., sorbitol, xylitol, pirocathechol, hydroquinone or -naphthol
• Centralyte and/or diphenylamine are mostly used as a stabilizer.
• the means contains a catalyst and/or an inhibitor of burning, and a cooling agent as a modifier of burning. It is desirable for regulation of FEAFM burning characteristics to the required level.
• the catalysts of burning are used for increasing of speed of burning and maintenance of burning stability at low pressure.
• the catalysts accelerate achievement of thermodynamic balance of oxidation reactions, those as
• the catalyst as a rule, there used compositions of metals of variable valence, e.g., oxides of iron, copper, nickel, cobalt, manganese, chrome; organic or inorganic compositions of same metals or mixtures thereof.
• the catalysts are added in FEAFM in quantity from 0.5 #to 10 mass parts, preferably 1-5 mass parts.
• Inhibitors of burning are added in FEAFM for reduction of their speed of burning, decreasing of temperature of surface burning and flame zone. Damping of chemical reactions of burning is achieved either due to blocking the active centers of flame (gas) reactions by inhibitors or products of their decomposition, or due to intensification of reactions of carbonization, resulting in forming on the surface of burning of dense and hard carbon carcass changing conditions of mass- and heat exchange on the border of gaseous and condensed phases. Due to the reaction
• phosphates of potassium, calcium, iron of any degree of displacement triphenyl phosphate; ammonium phosphates, ferric-ammonium phosphate, ammonium oxalate, ferric-ammonium oxalate; amides- carbamide, triazine and its derivatives, dicyanamide; among borates of metals - borates of potassium, sodium, calcium, magnesium, barium, zinc.
• Quantity of entered inhibitor comprises 5-30 mass parts, preferably 15-25 mass parts.
• the cooling agents are added in FEAFM for change of its thermal balance of burning. Additional reduction of temperature on the surface, and cooling of products of burning of FEAFM occurs due to physical removing of heat which is spent on heating of particles of the entered cooling agent, its endothermic decomposition, and also due to shielding of the thermal flow directed from the zone of flame reactions to the burning surface.
• cooling agent there are used oxides and hydroxides of metals of the II group, aluminosilicates, nepheline, metal shavings or mixtures thereof, or a heat- absorbing composition.
• Incombustible products of disintegration of the composition dilute products of FEAFM burning in the flame zone of reaction, reduce temperature of the flame and with it decrease return thermal flow to the surface of burning. Interaction of FEAFM combustion products with products of disintegration of the heat-absorbing composition results in "freezing" thereof, possibility of their further interaction is eliminated, in result, it is generated a cooled aerosol.
• Heat-absorbing composition includes the following ingredients, mass parts: heat-absorbing component 50-80 binder 10-35, additives 1-7, thus, as the heat-absorbing component there are mainly used carbonates or basic carbonates, phosphates of metals of the II group; crystal hydrides thereof, hydroxides of metals of the III group or mixtures thereof; as the binder derivatives of cellulose, e.g., nitrocellulose, plasticized by a low-volatile plasticizer , e.g., triacetin and/or dibutil phthalate, and polyvinyl acetate or polyvinyl alcohol; as the additive it is used lubricant oil, potassium or zinc stearate, organosilicon compositions and oleic acid.
• carbonates or basic carbonates phosphates of metals of the II group
• crystal hydrides thereof hydroxides of metals of the III group or mixtures thereof
• binder derivatives of cellulose e.g., nitrocellulose, plasticized by a low-volatile plastic
• quantity of the cooling agent can vary over a wide range from 0.5 to 250 mass parts .
• Lubricant oil composition chosen from the class of glycoles, or glycerin, salt of a fatty acid, e.g., potassium or zinc stearate or mixture thereof with sulforicinate and gelatin are used in FEAFM as the technological additives.
• FEAFM FEAFM of compositions from the class of glycoles such as diethylene glycol, triethylene glycol, or glycerin
• FEAFM FEAFM of compositions from the class of glycoles
• they are used in quantities from 0.1 to 2 mass parts as additional technological additives lowering external friction and the phenomenon of sticking to the technological equipment during manufacturing of FEAFM and processing thereof in various products (aerosol forming elements) .
• the best efficiency is shown with the technological additive including a triple mixture of: lubricant oil, diethylene glycol (triethylene glycol or glycerin) and a salt of a fatty acid.
• Diethylene glycol or triethylene glycol serves simultaneously as a plasticizer for cellulose derivatives, in particular, for nitrocellulose, and as an additive in small quantities (2-5 mass parts) to the base plasticizer it improves process of plasticization of nitrocellulose.
• Manufacturing of FEAFM is carried out by mixing of all components in required proportions in an apparatus having an agitator using a dry method or in water environment (for water insoluble nitrate plasticizers) at temperature 10- 55°C with subsequent forming from the received mixture of elements of necessary sizes and configuration at temperature 50-80°C.
• the fire extinguishing agent is added to the mixture pressed out of water.
• the cooling agent of heat-absorbing composition manufacturing thereof and forming of elements is carried out by the same way; in this case FEAFM is produced without cooling agent, and then it is performed mixing thereof or elements are used in layers.
• FEAFM fire extinguishing efficiency
• FEE of FEAFM compositions was extensively examined in laboratory and testing stand conditions at suppression of inflammable liquids (acetone, petrol, ethyl and isopropyl alcohols, mixture of diesel fuel with ' petrol) and was confirmed by tests of aerosol generators on their basis.
• the tested sample of FEAFM was placed in a metal housing and was fixed in the central part of the side wall of the chamber. Initiation of ignition of the FEAFM sample was performed using a fuse or a source of electric current located outside of the testing chamber. Petrol or another inflammable liquid in capacities was ignited, the cover of testing chamber was closed. After steady burning of inflammable liquid during 30 s it was initiated ignition of the FEAFM sample. And after 1 more minute the cover of chamber was opened and the chamber was inspected after dispersion of aerosol. Suppression or burning of inflammable liquid was defined with help of decoded oscillogramme records or visually through the windows in the chamber cover.
• FEAFM has the following structure of components (mass parts) :
• Source of carbon highly dispersed carbon 2.0
• Fuel-binder nitrocellulose 12.4 triacetine 9.0 polyvinyl acetate 2.0
• Fire extinguishing efficiency of FEAFM according to the laboratory method of estimation comprises 10 g/m 3 and in testing stand conditions according to the Standard UL 1058 - 25 g/m 3 .
• FEAFM has the following structure of components (mass parts) :
• Source of carbon highly dispersed carbon 2.0 Stabilizer : centralite 0.3 diphenyl-amine 0.7
• Technological additives diethylene glycol 1.0 lubricant (industrial) oil 1.0 sodium stearate 0.1
• This FEAFM was prepared similarly to example 1. Fire extinguishing efficiency the FEAFM according to the laboratory method of estimation comprises 10 g/m 3 and in testing stand conditions according to the Standard UL 1058
• FEAFM has the following structure of components (mass parts) :
• Source of carbon highly dispersed carbon 4.5 sorbitol 5.0
• Stabilizer centralite 0.5 diphenyl-amine 0.5
• Mixture of all components, except the flame suppressing agent and sorbitol, is performed in a mixer in a water environment at M 1:5 without additional heating of the equipment.
• nitrocellulose technological additives (lubricant oil, diethylene glycol, zinc stearate) and. modifiers of burning.
• It is prepared separately emulsion of mixture of plasticizers with stabilizers of chemical stability (centralite and diphenylamine) with addition of emulsifier - sulforicinate and emulsion stabilizer - gelatin.
• the emulsion is added into the mixer and contents of the mixer is mixed for 18-24 hours .
• the received mixture is squeezed out of water on a squeezing apparatus up to humidity of 10-16 mass % and further in an apparatus without mechanical mixers is mixed with the flame suppressing agent and sorbitol during 20-30 minutes .
• the ready mix is rolled and is formed into elements of required size in a hydraulic or an auger-press at temperature 60-80 ° C .
• Additives diethylene glycol 1.0 lubricant ⁇ industrial) oil 1.0 zinc stearate 0.1 Fuel-binder nitrocellulose 12 . 4 triacetine 9 . 0 polyvinyl acetate 2 . 0
• the obtained mixture is rolled at temperature 90-120 °C and formed on an auger-press into elements of required form and size.
• the obtained thus components of the means are mixed in the abovementioned ratio. Data on efficiency is specified in the table.
• Aerosol forming fire extinguishing composition according to the prior art is used in fire extinguishing devices together with a cooling agent with the purpose of obtaining a cooled flameless aerosol .
• Use of a cooling agent reduces efficiency (increases fire extinguishing concentration) due to settling of the aerosol in the layer of cooling agent. Fire extinguishing concentration in this case increases till 50-54 g/m 3 and more .
• Gasification character of FEAFM and large potential thereof for operational safety allows to use it as elements with highly developed surface, e.g., in the form of granules, that contributes to intensification of emitting of aerosol and faster filling the protected volume thereby, furthermore it is also economically favorable.
• a cooling agent in FEAFM in form of, e.g., metal shaving or minute elements of heat-absorbing composition, forming a mechanical mixture.
• the cooling agent in this case promotes formation of more loose structure of FEAFM, facilitating heat dissipation and simultaneously taking away additional amount of heat for self heating.
• the cooling agent amount is determined by chemical composition, size of used FEAFM elements, feature of application thereof and a number of other factors. In FEAFM without inhibitor the cooling agent contents can be high. Depending on the required purpose, e.g., on using of FEAFM in devices intended for explosion and fire protection of objects, it is reasonable to use the generated fire extinguishing aerosol in cold condition, i.e. temperature thereof should be below than temperature of self-ignition of explosive mixtures, therefore quantity of the cooling agent in FEAFM can make up to 250 mass parts.
• the proposed FEAFM depending on structure and the quantities of the modifier of burning are characterized by wide spectrum of variability of characteristics thereof.
• High speed of aerosol generation promotes fast filling of protected volume and fast creation of fire extinguishing concentration therein, that allows to use fire extinguishing devices on basis of such FEAFM in untight, ventilated or extended objects, e.g., in vehicles engine compartments, cable channels etc.
• FEAFM fire extinguishing devices on basis of such FEAFM
• the proposed invention considerably expands area of application of FEAFM due to the possibility of wide regulation of temperature of the generated fire extinguishing aerosol and speed of aerosol generation thereof, and can be used in various fire extinguishing devices, both with application of the cooling agent, and without it, which is a result of creation of FEAFM embodiments with steady flameless gasification not requiring additional cooling of the aerosol.
• FEAFM chemical, mechanical, technological etc.
• the area of application of the proposed FEAFM in fire extinguishing devices is characterized by the widest spectrum: all kinds of automobile-, railroad, aviation-, water transport, underground railway, warehouses of inflammable liquids and fuels and lubricants, enterprises of various branches of industry, including objects with explosive dust-gas-air environment and extended communication network of power supply, ventilation, etc.
• the means has low toxic level, is ozone safe, does not cause corrosion of metals, does not have destroying effect to material objects .

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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)
• Fireproofing Substances (AREA)
• Medicinal Preparation (AREA)
• Cosmetics (AREA)

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• 1998
  • 1998-09-11 RU RU98117411/12A patent/RU2146546C1/ru not_active IP Right Cessation
• 1999
  • 1999-08-03 AU AU53110/99A patent/AU754475B2/en not_active Ceased
  • 1999-08-03 CN CNB998119849A patent/CN1150046C/zh not_active Expired - Fee Related
  • 1999-08-03 EP EP99938680A patent/EP1109601B1/fr not_active Expired - Lifetime
  • 1999-08-03 AT AT99938680T patent/ATE231018T1/de not_active IP Right Cessation
  • 1999-08-03 CA CA002348644A patent/CA2348644A1/fr not_active Abandoned
  • 1999-08-03 DE DE69904950T patent/DE69904950T2/de not_active Expired - Lifetime
  • 1999-08-03 WO PCT/RU1999/000269 patent/WO2000015305A1/fr active IP Right Grant
  • 1999-08-03 BR BR9913567-1A patent/BR9913567A/pt not_active IP Right Cessation
  • 1999-08-11 MY MYPI99003441A patent/MY133539A/en unknown

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