US20010011567A1 - Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation - Google Patents
Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation Download PDFInfo
- Publication number
- US20010011567A1 US20010011567A1 US09/754,109 US75410901A US2001011567A1 US 20010011567 A1 US20010011567 A1 US 20010011567A1 US 75410901 A US75410901 A US 75410901A US 2001011567 A1 US2001011567 A1 US 2001011567A1
- Authority
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- United States
- Prior art keywords
- aerosol
- composition
- oxidizing agent
- gas
- weight
- Prior art date
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- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 46
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 13
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims abstract description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 235000013877 carbamide Nutrition 0.000 claims abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 229910002651 NO3 Inorganic materials 0.000 claims abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003513 alkali Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 32
- 239000002245 particle Substances 0.000 abstract description 31
- 239000000443 aerosol Substances 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 37
- 239000004323 potassium nitrate Substances 0.000 description 17
- 235000010333 potassium nitrate Nutrition 0.000 description 17
- 238000003825 pressing Methods 0.000 description 15
- 230000009467 reduction Effects 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 6
- OEMSKMUAMXLNKL-UHFFFAOYSA-N 5-methyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)=CCC2C(=O)OC(=O)C12 OEMSKMUAMXLNKL-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000009931 harmful effect Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-ZXXMMSQZSA-N D-iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 206010033307 Overweight Diseases 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 2
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000009828 non-uniform distribution Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000008275 solid aerosol Substances 0.000 description 2
- 239000006163 transport media Substances 0.000 description 2
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241000005139 Lycium andersonii Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000025865 Ulcer Diseases 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C99/00—Subject matter not provided for in other groups of this subclass
- A62C99/0009—Methods of extinguishing or preventing the spread of fire by cooling down or suffocating the flames
- A62C99/0018—Methods of extinguishing or preventing the spread of fire by cooling down or suffocating the flames using gases or vapours that do not support combustion, e.g. steam, carbon dioxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61D—VETERINARY INSTRUMENTS, IMPLEMENTS, TOOLS, OR METHODS
- A61D1/00—Surgical instruments for veterinary use
- A61D1/06—Castrating appliances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C5/00—Making of fire-extinguishing materials immediately before use
- A62C5/006—Extinguishants produced by combustion
Definitions
- the invention relates to fire-prevention, in particular to fire-extinguishing agents containing pyrotechnical compositions, which generate a fire-extinguishing aerosol formed as a result of the thermal decomposition of said compositions at combustion.
- Aerosol-forming compositions are used in fire-extinguishing systems for fires in enclosed and half-enclosed spaces, and namely in:
- the high molding pressure leads due to the increased surface friction between the particles of the solid fillers to the appearance of stress at the contact point of the particles, the formation of pores and, consequently, to a decrease of the stability and also to a non-uniform distribution of the particles in the molded composition, which leads to its non-uniform combustion and, as a consequence, to a decrease of the fire-extinguishing efficiency.
- a composition for extinguishing fires is known (RU 2001647), which contains as combustible binder an epoxide resin in an amount of 10-14.5% by weight, an isomethyltetrahydrophthalic anhydride curing agent in an amount of 12-15% by weight, potassium perchlorate in an amount of 2-25% by weight as oxidizing agent, as additives carbon or a pigment in an amount of 0.001-0.5% by weight, sulforicinate in an amount of 0.01-0.5% by weight, and potassium nitrate the balance.
- the fire-extinguishing concentration amounts to 23-27 g/m 3 .
- a composition for extinguishing fires is known (RU 2001648), which contains an epoxide resin in an amount of 1.5-15% by weight as combustible binder, isomethyltetrahydrophthalic anhydride in an amount of 1.5-15% by weight as curing agent, and additionally a polyether (polyester) resin in an amount of 7.5-30% by weight, methylethylketone peroxide in an amount of approximately 0.075% by weight, potassium perchlorate in an amount of 10-40% by weight as oxidizing agent, as additives sulforicinate or carbon in an amount of 0.001-0.5% by weight, and potassium nitrate the balance.
- a polyether (polyester) resin in an amount of 7.5-30% by weight
- methylethylketone peroxide in an amount of approximately 0.075% by weight
- potassium perchlorate in an amount of 10-40% by weight as oxidizing agent
- additives sulforicinate or carbon in an amount of 0.001-0
- the composition possesses an increased impact resistance if it contains the epoxy resin in an amount of 1.5% by weight and the polyether (polyester) resin in an amount of not more than 30% by weight. There exists also a lower content limit for the polyether (polyester) resin, i.e. 7.5% by weight, but in this case the epoxy resin must be present in an amount of up to 15% by weight.
- the process for the preparation of the compositions for extinguishing fires according to RU 2001647 and RU 2001648 comprises the steps of successive charging and mixing of the components of the composition. Said process comprises:
- the final composition is poured into forms and cured for 7-10 days at 80° C.
- an article of predetermined shape is obtained, which may be used for extinguishing fires by means of its ignition by an initiating system.
- compositions with a large content of solid phases because the reduction of the content of the binder leads to a drastic increase of the viscosity and the lack of flowability of the composition, furthermore, leads to difficulties in homogeneously dispersing the components and to an increase of the hazardness of the steps of mixing and molding articles from said composition.
- the use of high-weight portions of the binder in the composition leads to a low stability of the ignition and combustion of the composition, and also to a decrease of its fire-extinguishing efficiency;
- Pyrotechnical compositions for use in a process for extinguishing voluminous fires are known (EP 0561035 B1).
- the first composition contains potassium perchlorate in an amount of 40-50% by weight, epoxy resin in an amount of 9-12% by weight, potassium chloride in an amount of 10-44% by weight, and magnesium powder in an amount of up to 4% by weight.
- a second composition contains potassium nitrate in an amount of 70-80% by weight, epoxy resin in an amount of 19-23% by weight and magnesium or aluminium powder in an amount of 2-4% by weight.
- a composition for extinguishing fire and a process for its preparation are known (WO 92/17244) which contains alkali metal nitrate and/or perchlorate in an amount of 55-90% by weight, a combustible binder in an amount of 10-45% by weight, such as iditol or a ballistic propellant. Additionally, the composition may contain a combustible binder in an amount of 1-42% by weight, for example, dicyandiamide, and also ammonium perchlorate in an amount of 5-32% by weight as additional oxidizing agent.
- the process for preparing the composition is characterized in that the starting components (KNO 3 , iditol, dicyandiamide) are prepared by grinding large agglomerates of particles and subsequent mixing of the powdery substances in a predetermined proportion.
- the prepared mixture is subjected to a blind pressing step and afterwards may be used as fire-extinguishing agent.
- a high combustion temperature of the composition (approximately 1,000° C.);
- the pyrotechnical aerosol-forming composition for extinguishing fires and the process for its preparation as disclosed in RU 2101054 represents the closest prior art for the present invention.
- the composition contains as oxidizing agent potassium nitrate in an amount of 67-72% by weight, as combustible binder phenolformaldehyde resin in an amount of 8-12% by weight and as gas-aerosol-forming agent dicyandiamide representing the balance.
- the composition additionally may contain potassium bicarbonate or potassium benzoate or potassium hexacyanoferrate in an amount of 4-12% by weight.
- the process for the preparation of said pyrotechnical compositions comprises the step of mixing potassium nitrate with a specific surface area of its particles of no less than 1,500 cm 2 /g and the combustible binder being a phenolformaldehyde resin in admixture with ethanol and acetone in a ratio of 30-50:70-50. Afterwards, the solution is mixed with powdery potassium nitrate and the gas-aerosol-forming agent until a uniform distribution is achieved. Subsequently, the mixture is dried and granulated with simultaneously drying at a temperature of 20-70° C. until a residual content of moisture and volatile constituents of not more than 1% is present.
- the composition prepared according to such a process may be molded by means of blind pressing and used as a fire-extinguishing agent.
- a low combustion velocity of the composition (approximately 2.4 mm/s);
- a high combustion temperature of the composition (approximately 900° C.);
- a pyrotechnical gas-aerosol-forming composition for extinguishing fires which contains dicyandiamide as gas-aerosol-forming agent, which consists of particles of two fractions with 40-80 ⁇ m and 7-15 ⁇ m at a weight ratio of 80:20, potassium nitrate as oxidizing agent, which consists of particles of two fractions with 15-25 ⁇ m and 1-7 ⁇ m at a weight ratio of 25:75, a polycondensate of formaldehyde with organic compounds which are selected from the group consisting of phenol, melamine, carbamide as combustible binder, which consists of particles of two fractions with 70-120 ⁇ m and 10-25 ⁇ m at a weight ratio of 70:30, with the following content of the components in the mixture in % by weight: gas-aerosol-forming agent 9-20 combustible binder 6-14 oxidizing agent balance.
- the composition may contain as additive, which controls the combustion velocity, potassium chromate or potassium dichromate, or ammonium dichromate in an amount of 1.0-3.5% by weight, which are applied from aqueous solutions onto the surface of the oxidizing agent of the fraction of 1-7 ⁇ m, and as additive for the reduction of the combustion temperature graphite in an amount of 0.2-0.5% by weight, which is applied onto the surface of the oxidizing agent of the fraction of 15-25 ⁇ m.
- the solution of the above-mentioned technical problems concerning the present process for the preparation of pyrotechnical, gas-aerosol-forming compositions for extinguishing fires comprises the steps of mixing the powdery combustible binder, oxidizing agent and gas-aerosol-forming agent and subsequent molding, wherein at first the large sized fractions of the combustible binder with 70-120 ⁇ m, of the oxidizing agent with 15-25 ⁇ m and of the gas-aerosol-forming agent with 40-80 ⁇ m are mixed and subsequently their small-sized fractions with 10-25 ⁇ m, 1-7 ⁇ m and 7-15 ⁇ m are added to the obtained mixture.
- the process for preparing the aerosol-forming composition is carried out according to the embodiment, which comprises the steps of mixing a solution of the combustible binder, the oxidizing agent and the gas-aerosol-forming agent, subsequent drying, granulating with simultaneous drying and molding, then the mixing is carried out at first by combining the solution of the combustible binder with the large-sized fractions of the oxidizing agent and the gas-aerosol-forming agent, and afterwards, correspondingly their small-sized fractions are combined.
- the heat front propagates within its volume and causes the thermal decomposition of the components including the oxidizing agent.
- the ions of chrome catalyze the decomposition of the oxidizing agent, which leads to an increased linear combustion velocity of the composition. Due to the fact that the chrome compounds are distributed on the surface and directly in the zone of the heated oxidizing agent, the efficiency of their catalytical effect increases.
- a further possibility to influence the fire-extinguishing characteristics of the composition consists in the application of graphite in an amount of 0.2-0.5% by weight on the surface of the large-sized oxidizing agent fraction within 15-25 ⁇ m prior to the mixing step of their components.
- Graphite may be applied to the surface by mixing with the oxidizing agent, or at the stage of grinding or by sieving the oxidizing agent through a fractionating sieve.
- the application of the dichromate to the potassium nitrate surface is carried out in a blade mixer by adding dropwise a 50% aqueous solution of potassium dichromate to the potassium nitrate under stirring, which is accomplished within 1 hour. Afterwards, the modified potassium nitrate is poured out on a tray and placed in a drying oven at a temperature of 80° C. for 2 hours until the weight portion of the moisture is less than 0,1%.
- the pressing is carried out in one pressing step with a velocity of 0,003 m/s, wherein the pressure is maintained for 5 seconds until the end of the pressing.
- a blade mixer For the preparation of 1 kg of the composition, a blade mixer is charged with 183,3 g of a 60% solution of phenolformaldehyde resin in ethanol. This amounts to 110 g when calculated on the basis of phenolformaldehyde resin.
- the solution is prepared in a reactor equipped with a water-jacket for heating up to +50° C. and a stirrer rotating with a velocity of 85 rpm.
- the solution time is 1 hour.
- the prepared solution does not contain residual undissolved resin.
- the prepared composition is placed in a granulator, supplied with calibrated outlet measures with a diameter of 1.2-2 mm. After passage through said measures, granulates of the composition are obtained which have a length up to 3 mm and a weight ratio of the components: dicyandiamide—19 ⁇ 0,5% by weight, potassium nitrate—70 ⁇ 0,5% by weight, and formaldehyde resin—11 ⁇ 0,5% by weight.
- tablets are formed by the method of blind pressing.
- the specific pressing pressure is 1000 kgf/cm 2 (100 MPa).
- the pressing is carried out in one pressing step with a velocity of 0,003 m/s, wherein the pressure is maintained for 5 seconds until the end of the pressing.
- Examples Nos. 1 and 2 of the Table are prepared according to the procedure of embodiment 2.
- Examples Nos. 6 and 7 of the Table are prepared according to RU 2101054 and WO 92/17244, respectively.
- the final composition is subjected to tests according to standard methods. Upon combustion the linear combustion velocity, the fire-extinguishing concentration, the combustion temperature, the weight portion of the disperse phase of the aerosol, the weight portion of the particles with 1-2 ⁇ m in the composition of the disperse phase of the aerosol are determined.
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- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Surgery (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Air Bags (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
The invention relates to fire-extinguishing technology, in particular to pyrotechnical compositions for extinguishing fires and processes for their preparation.
The invention allows to prepare pyrotechnical, aerosol-forming compositions with predetermined physico-mechanical properties, increased combustion velocity, reduced combustion temperature and large weight portion of solid particles with 1-2 μm in the aerosol.
The pyrotechnical, aerosol-forming composition for extinguishing fires contains: as gas-aerosol-forming agent 2 fractions of dicyandiamide with 40-80 μm and 7-15 μm at a weight ratio of 80:20, as combustible binder 2 fractions of a polycondensate of formaldehyde with an organic compound, which is preferable selected from the group consisting of melamine, carbamide and phenol, with 70-120 μm and 10-25 μm at a weight ratio of 70:30, as oxidizing agent 2 fractions of an alkali nitrate with 15-25 μm and 1-7 μm with the following content of the components in % by weight:
Gas-aerosol-forming agent 9-20
Combustible binder 6-14
Oxidizing agent the balance.
The process for preparing the composition comprises the steps of pre-application of potassium chromate, potassium dichromate or ammonium dichromate, graphite on the surface of the oxidizing agent and the mixing of the components in a predetermined succession.
The invention may be used in fire-extinguishing technology.
Description
- The invention relates to fire-prevention, in particular to fire-extinguishing agents containing pyrotechnical compositions, which generate a fire-extinguishing aerosol formed as a result of the thermal decomposition of said compositions at combustion.
- Aerosol-forming compositions are used in fire-extinguishing systems for fires in enclosed and half-enclosed spaces, and namely in:
- warehouses and garages;
- office and factory rooms;
- sections of transport media such as land vehicles, ocean-going and river ships, aeroplanes;
- air-ventilator systems, etc.
- Fire-extinguishing compositions must meet a whole complex of requirements:
- a high fire-extinguishing efficiency;
- a low toxicity of the combustion products;
- a low temperature of the combustion products;
- a simple, safe and low energy consuming preparation technology;
- durability of the composition.
- The maintenance of all the requirements interferes with the problems concerning the reciprocal, often conflicting with one another, effects of the factors related to the technology of preparation of fire-extinguishing compositions and their characteristics. For example, the requirement of high fire-extinguishing efficiency makes it necessary to use a large amount of solid fillers (oxidizing agents, combustible agents) in the compositions. However, the increase of the portion of solid fillers leads to an increased molding pressure, which in turn increases the hazardness of the process and its energy capacity. The high molding pressure leads due to the increased surface friction between the particles of the solid fillers to the appearance of stress at the contact point of the particles, the formation of pores and, consequently, to a decrease of the stability and also to a non-uniform distribution of the particles in the molded composition, which leads to its non-uniform combustion and, as a consequence, to a decrease of the fire-extinguishing efficiency.
- For the development of novel compositions and the improvement of known compositions, the problem is said to meet the sum of present requirements or to significantly improve separate properties and characteristics.
- A composition for extinguishing fires is known (RU 2001647), which contains as combustible binder an epoxide resin in an amount of 10-14.5% by weight, an isomethyltetrahydrophthalic anhydride curing agent in an amount of 12-15% by weight, potassium perchlorate in an amount of 2-25% by weight as oxidizing agent, as additives carbon or a pigment in an amount of 0.001-0.5% by weight, sulforicinate in an amount of 0.01-0.5% by weight, and potassium nitrate the balance. When said composition is used, the fire-extinguishing concentration amounts to 23-27 g/m3.
- A composition for extinguishing fires is known (RU 2001648), which contains an epoxide resin in an amount of 1.5-15% by weight as combustible binder, isomethyltetrahydrophthalic anhydride in an amount of 1.5-15% by weight as curing agent, and additionally a polyether (polyester) resin in an amount of 7.5-30% by weight, methylethylketone peroxide in an amount of approximately 0.075% by weight, potassium perchlorate in an amount of 10-40% by weight as oxidizing agent, as additives sulforicinate or carbon in an amount of 0.001-0.5% by weight, and potassium nitrate the balance. The composition possesses an increased impact resistance if it contains the epoxy resin in an amount of 1.5% by weight and the polyether (polyester) resin in an amount of not more than 30% by weight. There exists also a lower content limit for the polyether (polyester) resin, i.e. 7.5% by weight, but in this case the epoxy resin must be present in an amount of up to 15% by weight.
- The process for the preparation of the compositions for extinguishing fires according to RU 2001647 and RU 2001648 comprises the steps of successive charging and mixing of the components of the composition. Said process comprises:
- Charging of the binder and the curing agent (epoxy resin and isomethyltetrahydrophthalic anhydride, and according to RU 2001648 additionally the polyether (polyester) resin and methylethylketone peroxide) and mixing within 30 minutes at a temperature of 20° C. with evacuation.
- Charging of two doses of alkali metal nitrate with mixing for 10 minutes.
- Charging of two doses of alkali metal perchlorate with mixing for 10 minutes and subsequent mixing of the components for 1 hour.
- Charging of carbon or sulforicinate and mixing of all components for 30 minutes, whereby the last 20 minutes are carried out with evacuation.
- The final composition is poured into forms and cured for 7-10 days at 80° C.
- As a result, an article of predetermined shape is obtained, which may be used for extinguishing fires by means of its ignition by an initiating system.
- Said compositions and the process for their preparation possess a series of essential disadvantages:
- a high-energy capacity of the process due to the use of the epoxy resin with isomethyltetrahydrophthalic anhydride, which requires a prolonged curing of the composition (7-10 days at 80° C.). The use of polyethylene polyamine as curing agent allows to significantly (up to 1 hour) reduce the curing time, but at the same time there occurs an increase of the dynamic viscosity with such a velocity that it is not possible to prepare the composition at an industrial scale due to the loss of “survivability” at the stage of processing;
- ecological hazardness due to the presence of uncured epoxy resin and isomethyltetrahydrophthalic anhydride in the composition, which may cause dermatitis and ulcers, if said components come in contact with the skin;
- limited possibility to prepare compositions with a large content of solid phases (oxidizing agent, gas-aerosol-forming agent), because the reduction of the content of the binder leads to a drastic increase of the viscosity and the lack of flowability of the composition, furthermore, leads to difficulties in homogeneously dispersing the components and to an increase of the hazardness of the steps of mixing and molding articles from said composition. The use of high-weight portions of the binder in the composition leads to a low stability of the ignition and combustion of the composition, and also to a decrease of its fire-extinguishing efficiency;
- the necessity to take additional steps in order to ensure the safeness during the processing of the composition for the case that methylethyleketone peroxide, which appears to be an explosive substance, is used in the composition. Furthermore, the provision of a stable composition is only possible in a narrow range of the proportion of epoxy resin and polyether (polyester) resin and correspondingly their curing agents, which affords very high demands on the accuracy of the dosing of the components and the necessity to observe a strict succession of the addition of the components;
- a high dependence of the technological parameters (viscosity, flowability) of the composition and its fire-extinguishing concentration on minor changes in the preparation conditions and the concentration of the components. Thus, a change of the carbon content in the composition from 0.6 to 0.45% by weight leads to an increase of the viscosity by a factor of 103 (from 2×103 poise to 8×106 poise) and a decrease of the flowability coefficient (from 0.8 to 0.05), whereas the fire-extinguishing concentration increases from 24 to 27 g/m3.
- Pyrotechnical compositions for use in a process for extinguishing voluminous fires are known (EP 0561035 B1). The first composition contains potassium perchlorate in an amount of 40-50% by weight, epoxy resin in an amount of 9-12% by weight, potassium chloride in an amount of 10-44% by weight, and magnesium powder in an amount of up to 4% by weight. A second composition contains potassium nitrate in an amount of 70-80% by weight, epoxy resin in an amount of 19-23% by weight and magnesium or aluminium powder in an amount of 2-4% by weight.
- Said pyrotechnical compositions possess several essential disadvantages:
- A high temperature of the combustion products;
- harmful effect on living organisms of chlorine derivatives, which are present in the combustion products, and base (KOH), which, moreover, condensates on the surface of high-precision devices and similar equipments and may lead to corrosion;
- harmful effect on living organisms of solid aerosol particles with a size of up to 1 μm, which irritate the mucous membrane of respiratory tracts, penetrate into blood vessels and practically do not move out of the organism.
- A composition for extinguishing fire and a process for its preparation are known (WO 92/17244) which contains alkali metal nitrate and/or perchlorate in an amount of 55-90% by weight, a combustible binder in an amount of 10-45% by weight, such as iditol or a ballistic propellant. Additionally, the composition may contain a combustible binder in an amount of 1-42% by weight, for example, dicyandiamide, and also ammonium perchlorate in an amount of 5-32% by weight as additional oxidizing agent.
- The process for preparing the composition is characterized in that the starting components (KNO3, iditol, dicyandiamide) are prepared by grinding large agglomerates of particles and subsequent mixing of the powdery substances in a predetermined proportion. The prepared mixture is subjected to a blind pressing step and afterwards may be used as fire-extinguishing agent.
- Said composition and process for its preparation possess several essential disadvantages:
- a low gas-aerosol-formation velocity due to a low linear combustion velocity of the composition (approximately 1.5 mm/s);
- a low fire and explosion safety and high energy capacity of the preparation process due to a high specific pressing pressure (approximately 2,000 kgf/cm2);
- a high combustion temperature of the composition (approximately 1,000° C.);
- unstable conditions of the ignition and combustion of the composition due to a difference in vertical density and due to different stability properties in the total composition.
- The pyrotechnical aerosol-forming composition for extinguishing fires and the process for its preparation as disclosed in RU 2101054 represents the closest prior art for the present invention. The composition contains as oxidizing agent potassium nitrate in an amount of 67-72% by weight, as combustible binder phenolformaldehyde resin in an amount of 8-12% by weight and as gas-aerosol-forming agent dicyandiamide representing the balance. The composition additionally may contain potassium bicarbonate or potassium benzoate or potassium hexacyanoferrate in an amount of 4-12% by weight.
- The process for the preparation of said pyrotechnical compositions comprises the step of mixing potassium nitrate with a specific surface area of its particles of no less than 1,500 cm2/g and the combustible binder being a phenolformaldehyde resin in admixture with ethanol and acetone in a ratio of 30-50:70-50. Afterwards, the solution is mixed with powdery potassium nitrate and the gas-aerosol-forming agent until a uniform distribution is achieved. Subsequently, the mixture is dried and granulated with simultaneously drying at a temperature of 20-70° C. until a residual content of moisture and volatile constituents of not more than 1% is present. The composition prepared according to such a process may be molded by means of blind pressing and used as a fire-extinguishing agent.
- This composition and process for its preparation possess several essential disadvantages:
- a high specific pressing pressure (approximately 1,400 kgf/cm2) due to a high surface friction between the solid particles of the fillers;
- a low combustion velocity of the composition (approximately 2.4 mm/s);
- a high combustion temperature of the composition (approximately 900° C.);
- a non-uniform distribution of special additives present in low amounts (combustion catalysts, technological additives), which leads to insufficiently effective utilization of said additives at the stage of preparing the composition and at its combustion;
- harmful effects on living organisms and high weight portions of aerosol particles with a size of less than 1 μm (approximately 27% by weight), which penetrate through the mucous membrane into the blood vessels and practically do not move out of the organism and result in the formation of thrombi with a subsequent negative effect on life of the organism.
- The technical problems which are solved by the present invention are the following:
- reduction of the specific molding pressure and reduction of the hazardness and energy capacity of the process for the preparation of the composition;
- increase of the combustion velocity of the composition and correspondingly increasing the velocity of the gas-aerosol-formation;
- reduction of the combustion temperature of the composition;
- increase of the uniformity of the distribution of the additives present in small concentrations and increase of their efficiency;
- increase of the weight portion of the aerosol particles with a size of 1-2 μm due to a reduction of the portion of the particles with a size less than 1 μm and consequently increase of the ecological purity of the pyrotechnical composition.
- These technical problems were solved by a pyrotechnical gas-aerosol-forming composition for extinguishing fires, which contains dicyandiamide as gas-aerosol-forming agent, which consists of particles of two fractions with 40-80 μm and 7-15 μm at a weight ratio of 80:20, potassium nitrate as oxidizing agent, which consists of particles of two fractions with 15-25 μm and 1-7 μm at a weight ratio of 25:75, a polycondensate of formaldehyde with organic compounds which are selected from the group consisting of phenol, melamine, carbamide as combustible binder, which consists of particles of two fractions with 70-120 μm and 10-25 μm at a weight ratio of 70:30, with the following content of the components in the mixture in % by weight:
gas-aerosol-forming agent 9-20 combustible binder 6-14 oxidizing agent balance. - The composition may contain as additive, which controls the combustion velocity, potassium chromate or potassium dichromate, or ammonium dichromate in an amount of 1.0-3.5% by weight, which are applied from aqueous solutions onto the surface of the oxidizing agent of the fraction of 1-7 μm, and as additive for the reduction of the combustion temperature graphite in an amount of 0.2-0.5% by weight, which is applied onto the surface of the oxidizing agent of the fraction of 15-25 μm.
- The solution of the above-mentioned technical problems concerning the present process for the preparation of pyrotechnical, gas-aerosol-forming compositions for extinguishing fires comprises the steps of mixing the powdery combustible binder, oxidizing agent and gas-aerosol-forming agent and subsequent molding, wherein at first the large sized fractions of the combustible binder with 70-120 μm, of the oxidizing agent with 15-25 μm and of the gas-aerosol-forming agent with 40-80 μm are mixed and subsequently their small-sized fractions with 10-25 μm, 1-7 μm and 7-15 μm are added to the obtained mixture.
- If the process for preparing the aerosol-forming composition is carried out according to the embodiment, which comprises the steps of mixing a solution of the combustible binder, the oxidizing agent and the gas-aerosol-forming agent, subsequent drying, granulating with simultaneous drying and molding, then the mixing is carried out at first by combining the solution of the combustible binder with the large-sized fractions of the oxidizing agent and the gas-aerosol-forming agent, and afterwards, correspondingly their small-sized fractions are combined.
- In this way a packing of the components' particles is formed, wherein the large particles form the framework, and the smaller particles fill into the intermediate space between them. In the process for the preparation of the composition between the solid particles, layers of the combustible binder are built up, which cover the solid particles and provide good conditions for the movement of the particles of the composition in the flow at the application of stress, which contribute to the reduction of the molding pressure, the reduction of hazardness, and also the reduction of the energy capacity at the preparation of the composition. Due to the effective packing of particles with different sizes, sites with stressed structure are practically absent in the composition, which leads to a high, long-lasting stability of the strength characteristics, which, in turn, leads to an equalizing of the velocity gradient when the composition is combusted in layers, and the realization of values of the total linear combustion velocity of the composition.
- Due to the efficient packing of the components' particles it is possible to increase the weight portion of the particles of the oxidizing agent (up to 85% by weight), which leads to an increase of the weight portion of the solid aerosol phases, which form at the combustion of the composition. For the case that melamineformaldehyde or carbamideformaldehyde resins, which are prepared by polycondensation, are used in the composition as combustible binder, it is possible to increase the weight portion of the particles with 1-2 μm in the aerosol composition due to a reduction of the portion of the particles with less than 1 μm. This leads to an increase of the ecological purity of the fire-extinguishing aerosol. Hitherto, the use of such binders, which contain a huge amount of bound nitrogen, in pyrotechnical aerosol-forming compositions was not known. At the thermal decomposition of these binders, the portion of free inert gas, i.e. nitrogen, is increased and at the same time the portions of harmful, carbon-containing gases CO and CO2 are reduced.
- It was not possible to expect in advance or predict the obtained technical results, if the known methods for estimation of the optimal functions of particle size distribution were used for variants of different packings (V. V. Moshew, V. A. Ivanov, Reologicheskoye povedenye concentrirovannykh nonnewtonnovskykh suspensykh [Rheological Behavior of Concentrated Non-Newton Suspensions], M.: Nauka, 1990). In the present case, it was not possible to use said approaches, because they would have led to in advance incorrect results in the case of multi-component compositions and multi-functional, physico-chemical factors. In the composition three types of particles are used, which are different in their physico-chemical nature and show different effects on one another not only at the stage of preparation and processing of the composition but also when the composition is directly used for extinguishing a fire.
- For further increasing the linear combustion velocity of the composition, it is necessary, prior to the mixing step, to apply potassium chromate or potassium dichromate or ammonium dichromate in an amount of 1.0-3.5% by weight from an aqueous solution onto the surface of the small-sized oxidizing agent fraction with 1-7 μm and to dry the treated oxidizing agent until constant weight. The application of the additives onto the surface is carried out by simply adding dropwise the solution under stirring to the oxidizing agent. The aqueous solution wets the oxidizing agent. When the moisture is removed the additive is retained on the surface due to physical thin film adsorption forces. The following steps of the preparation process are carried out as described above. At the ignition of the composition the heat front propagates within its volume and causes the thermal decomposition of the components including the oxidizing agent. The ions of chrome catalyze the decomposition of the oxidizing agent, which leads to an increased linear combustion velocity of the composition. Due to the fact that the chrome compounds are distributed on the surface and directly in the zone of the heated oxidizing agent, the efficiency of their catalytical effect increases.
- A further possibility to influence the fire-extinguishing characteristics of the composition, namely the reduction of the combustion temperature of the composition, consists in the application of graphite in an amount of 0.2-0.5% by weight on the surface of the large-sized oxidizing agent fraction within 15-25 μm prior to the mixing step of their components. Graphite may be applied to the surface by mixing with the oxidizing agent, or at the stage of grinding or by sieving the oxidizing agent through a fractionating sieve.
- Under small shearing forces graphite disintegrates and may easily be applied to the surface. The surface modification of the oxidizing agent with graphite gives the oxidizing agent and the whole composition hydrophobic properties and reduces the hygroscopicity of the latter, which is very important for achieving a long-lasting stability of the fire-extinguishing composition. At the same time, graphite as a lubricant reduces the surface friction of the solid particles, in particular the large-size particles, which build up the framework of the composition. As a result, the molding pressure, the explosion hazard and the energy capacity of the preparation process of the composition are reduced. However, the most important merit of graphite as additive is characterized in that it is located directly on the heated layer of the decomposed potassium nitrate and diffuses into the gas zone of the flame, where it interacts with the decomposition products of the gas-aerosol forming agent, the combustible binder, namely with CO2 and H2O, and enters into endothermic reactions under withdrawal of heat with these products:
C + 2H2O → CO2 + 2H2 −178,15 kJ C + CO2 → 2CO −172,45 kJ C + H2O → CO + H2 −175,30 kJ - This leads to a reduction of the temperature of the combustion products of the composition.
- A comparative analysis of the present pyrotechnical gas-aerosol-forming agent for extinguishing fires and the present process for its preparation with the closest prior art documents revealed the following distinguishing features:
- Use of the oxidizing agent in the form of two fractions with 15-25 μm and 1-7 μm at a weight ratio of 25:75;
- Use of the gas-aerosol-forming agent in the form of two fractions with 40-80 μm and 7-15 μm at a weight ratio of 80:20;
- Use of the combustible binder in the form of two fractions with 70-120 μm and 10-25 μm at a weight ratio of 70:30;
- Use of a polycondensate of formaldehyde and melamine (2,4,6-triamino-1,3,5-triazine) or carbamide (NH2)2CO (melamineformaldehyde and carbamideformaldehyde resins) as combustible binder;
- Use of chrome compounds applied to the surface of the oxidizing agent fraction with 1-7 μm in an amount of 1,0:3,5 % by weight;
- Use of graphite applied to the surface of the oxidizing agent fraction with 15-25 μm;
- The step of mixing the components by successive dispersion of the oxidizing agent fraction with 15-25 μm and the gas-aerosol-forming agent fraction with 40-80 μm in the combustible binder and subsequent addition of their fractions with 1-7 μm and 7-15 μm to the obtained mixture.
- Preferred embodiments of the invention
- Embodiment 1
- For the preparation of 1 kg of the composition a blade mixer is charged with 77 g of a phenolformaldehyde resin fraction with 70-120 μm. Under stirring, 165 g of a potassium nitrate fraction with 15-25 μm are added, to the surface of which 5 g graphite have been previously applied. The application of graphite to the surface of the oxidizing agent is carried out by mixing them in a blade mixer and subsequently passing the modified oxidizing agent twice through a metal sieve with a mesh size of 40 μm.
- Afterwards, 152 g of a dicyandiamide fraction with 40-80 μm are added, stirred for 5 minutes, and 495 g of a potassium nitrate fraction with 1-7 μm are added, to the surface of which potassium dichromate in an amount of 35 g have previously been applied.
- The application of the dichromate to the potassium nitrate surface is carried out in a blade mixer by adding dropwise a 50% aqueous solution of potassium dichromate to the potassium nitrate under stirring, which is accomplished within 1 hour. Afterwards, the modified potassium nitrate is poured out on a tray and placed in a drying oven at a temperature of 80° C. for 2 hours until the weight portion of the moisture is less than 0,1%.
- 33 g of a phenolformaldehyde fraction with 10-25 μm are added under stirring to the obtained powdery mass, and afterwards 38 g of a dicyandiamide fraction with 7-15 μm are added and finally stirred for 15 minutes. The final composition is a powdery material of white color with a yellowish shade, which is molded by blind pressing. For the present composition, which corresponds to No. 3 of the Table, the specific pressing pressure is 1200 kgf/cm2 (120 MPa).
TABLE Comparative characteristics of the present pyrotechnical aerosol-forming compositions and known compositions Name of the Components of the Present Composition Composition Content of the Components, % by wt. 1) 2) Example No. 1 2 3 4 5 6 7 Potassium nitrate 69.0 69.7 66.0 70.0 — 70 70 Sodium nitrate — — — — 70.0 Dicyandiamide 19 19 19 19 19 19 19 Phenolformaldehyde — 11 11 11 11 11 11 resin Melamineformaldehyde resin 11 — — — — — — Carbamideformaldehyde resin — 11 — — — — Potassium dichromate 1.0 — 3.5 — — — — applied onto the surface of small-sized potassium nitrate fraction Graphite applied — 0.3 0.5 — — — — onto the surface of the potassium nitrate fraction Designation of the characteristics of the composition Specific pressing 1000 980 1200 1000 990 1400 2000 pressure, kgf/cm2 Linear combustion 3.5 3.1 4.0 3.2 3.0 2.1. 1.5 velocity, mm/s Weight portion of 68 69 70 70 71 57 48 the dispersed phase of the aerosol, % Weight portion of 70 71 70 70 71 64 57 the particles with 1-2 μm in the composition of the dispersed phase of the aerosol, % Fire-extinguishing 34 33 32 32 33 40 50 concentration, g/m3 Combustion temperature, ° C. 640 620 650 720 750 890 950 - The pressing is carried out in one pressing step with a velocity of 0,003 m/s, wherein the pressure is maintained for 5 seconds until the end of the pressing.
- Embodiment 2
- For the preparation of 1 kg of the composition, a blade mixer is charged with 183,3 g of a 60% solution of phenolformaldehyde resin in ethanol. This amounts to 110 g when calculated on the basis of phenolformaldehyde resin.
- The solution is prepared in a reactor equipped with a water-jacket for heating up to +50° C. and a stirrer rotating with a velocity of 85 rpm. The solution time is 1 hour. The prepared solution does not contain residual undissolved resin.
- To the indicated amount of solution, 175 g of the potassium nitrate fraction with 15-25 μm are added as oxidizing agent, stirred for 5 minutes. Afterwards, 152 g of the dicyandiamide fraction with 40-80 μm are added as gas-aerosol-forming agent under stirring. After 5 minutes of stirring, 525 g of the potassium nitrate fraction with 1-7 μm are added and stirred for 10 minutes. Then 38 g of the dicyandiamide fraction with 7-15 μm are added and stirred for 10 minutes. Afterwards, the drying of the composition is carried out under rotating blades by ventilating it with air at room temperature and an excessive pressure of 1 kg/cm2 for 15 minutes.
- The prepared composition is placed in a granulator, supplied with calibrated outlet measures with a diameter of 1.2-2 mm. After passage through said measures, granulates of the composition are obtained which have a length up to 3 mm and a weight ratio of the components: dicyandiamide—19±0,5% by weight, potassium nitrate—70±0,5% by weight, and formaldehyde resin—11±0,5% by weight.
- The obtained granules of the composition are placed on trays, which are placed in a drying oven at a temperature of +45° C. After drying, exactly for a period of 4 hours, the content of the residual volatile components does not exceed 0,8% by weight.
- From the obtained dry granules of the composition, tablets are formed by the method of blind pressing. For the present composition, which corresponds to No. 4 of the Table, the specific pressing pressure is 1000 kgf/cm2 (100 MPa). The pressing is carried out in one pressing step with a velocity of 0,003 m/s, wherein the pressure is maintained for 5 seconds until the end of the pressing. Examples Nos. 1 and 2 of the Table are prepared according to the procedure of embodiment 2. Examples Nos. 6 and 7 of the Table are prepared according to RU 2101054 and WO 92/17244, respectively.
- The final composition is subjected to tests according to standard methods. Upon combustion the linear combustion velocity, the fire-extinguishing concentration, the combustion temperature, the weight portion of the disperse phase of the aerosol, the weight portion of the particles with 1-2 μm in the composition of the disperse phase of the aerosol are determined.
- The obtained values are presented in the Table.
- Industrial use
- The present composition for extinguishing fires and the process for its preparation allow to effectively extinguish fires of different burning materials in buildings and devices such as:
- warehouses, garages, working places;
- offices, places for keeping animals and birds;
- motor and luggage sections of transport media;
- ventilator systems of production plants, hotels, etc.
- The advantages of the present composition and process for its preparation are the following:
- ease and safety of the preparation process, durability and reliability during use, high fire-extinguishing efficiency, a broad base of raw materials for the components of the composition and the possibility to use easily available equipment for the performance of the preparation process, low pressure for molding an article from the composition, low combustion temperature, furthermore, the fire-extinguishing, gas-aerosol mixture does not show an injurious effect on human beings and living organisms surrounding them, the nature, and high-precision devices and systems.
Claims (7)
1. Pyrotechnical, aerosol-forming composition for extinguishing fires, containing dicyandiamide as gas-aerosol-forming agent, a polycondensate of formaldehyde and an organic compound as combustible binder and an alkali nitrate as oxidizing agent, characterized in that the gas-aerosol-forming agent, the combustible binder and the oxidizing agent consist of two fractions: 40-80 μm and 7-15 μm at a weight ratio of 80:20, 70-120 μm and 10-25 μm at a weight ratio of 70:30, 15-25 μm and 1-7 μm at a weight ratio of 25:75, respectively, with the following content of the components in % by weight:
gas-aerosol-forming agent 9-20
combustible binder 6-14
oxidizing agent the balance.
2. Composition according to , characterized in that it contains a polycondensate of formaldehyde and melamine or carbamide as combustible binder.
claim 1
3. Composition according to , characterized in that it contains a phenolformaldehyde resin as combustible binder.
claim 1
4. Process for the preparation of the pyrotechnical, gas-aerosol-forming compositions for extinguishing fires according to any of to , comprising the steps of mixing the combustible binder, the oxidizing agent and the gas-aerosol-forming agent in powder-form and molding of the mixture, characterized in that at first the fraction of the combustible binder with 70-120 μm is mixed with the fraction of the oxidizing agent with 10-25 μm and the fraction of the gas-aerosol-forming agent with 40-80 μm, and subsequently their fractions with 10-25 μm, 1-7 μm and 7-15 μm are added to the obtained mixture.
claims 1
3
5. Process for the preparation of the pyrotechnical, aerosol-forming compositions for extinguishing fires according to any of to , comprising the steps of mixing a solution of the combustible binder, the oxidizing agent and the gas-aerosol-forming agent, and subsequently drying, granulating with drying and molding, characterized in that the mixing is carried out by dispersing the fraction of the oxidizing agent with 15-25 μm and the fraction of the gas-aerosol-forming agent with 40-80 μm in a solution of the combustible binder, and subsequently their fractions with 1-7 μm and 7-15 μm are added to the obtained mixture.
claims 1
3
6. Process according to any of claims 4-5, characterized in that prior to the step of mixing potassium chromate or potassium dichromate or ammonium dichromate is applied in an amount of 1,0-3,5 wt. % from an aqueous solution onto the surface of the oxidizing agent of the fraction with 1-7 μm, and subsequently dried until constant weight is reached.
7. Process according to any of claims 4-6, characterized in that prior to the step of mixing graphite is applied in an amount of 0,2-0,5 wt. % onto the surface of the oxidizing agent of the fraction with 15-25 μm.
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US09/754,109 US20010011567A1 (en) | 1998-07-30 | 2001-01-05 | Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation |
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RU98113952/12A RU2147903C1 (en) | 1998-07-30 | 1998-07-30 | Composition for pyrotechnic aerosol-forming fire-extinguishing formulation and method for preparing aerosol-forming fire- extinguishing formulation |
US09/294,716 US6264772B1 (en) | 1998-07-30 | 1999-04-20 | Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation |
US09/754,109 US20010011567A1 (en) | 1998-07-30 | 2001-01-05 | Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation |
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US09/294,716 Expired - Lifetime US6264772B1 (en) | 1998-07-30 | 1999-04-20 | Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation |
US09/754,109 Abandoned US20010011567A1 (en) | 1998-07-30 | 2001-01-05 | Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/294,716 Expired - Lifetime US6264772B1 (en) | 1998-07-30 | 1999-04-20 | Pyrotechnical, aerosol-forming composition for extinguishing fires and process for its preparation |
Country Status (8)
Country | Link |
---|---|
US (2) | US6264772B1 (en) |
EP (1) | EP0976424B1 (en) |
AU (1) | AU762661B2 (en) |
BR (1) | BR9903014A (en) |
CA (1) | CA2270027C (en) |
DE (2) | DE19914780C2 (en) |
NO (1) | NO312909B1 (en) |
RU (1) | RU2147903C1 (en) |
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US20100078098A1 (en) * | 2002-08-05 | 2010-04-01 | Daicel Chemical Industries, Ltd. | Gas generating composition for inflator containing melamine cyanurate |
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US20120034482A1 (en) * | 2010-08-06 | 2012-02-09 | Atoz Design Labs Co., Limited | Fire extinguishing material and fabrication method thereof |
US20120273711A1 (en) * | 2010-01-19 | 2012-11-01 | Shaanxi J & R Fire Fighting Co. Ltd. | Novel aging-resistant aerosol generating agent and a preparation method thereof |
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RU2046614C1 (en) | 1991-04-08 | 1995-10-27 | Всесоюзный научно-исследовательский институт противопожарной обороны | Device for detection and volumetric suppression of fire and smoke-forming compound |
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RU2095102C1 (en) * | 1996-04-24 | 1997-11-10 | Специальное конструкторско-технологическое бюро "Технолог" | Device for detection and volume extinguishing the fire and aerosol-forming fire-extinguishing compound |
DE19636725C2 (en) * | 1996-04-30 | 1998-07-09 | Amtech R Int Inc | Method and device for extinguishing room fires |
RU2101054C1 (en) * | 1996-04-30 | 1998-01-10 | Закрытое акционерное общество "Техно-ТМ" | Aerosol-forming composition for fire extinguishing and a method of its making |
-
1998
- 1998-07-30 RU RU98113952/12A patent/RU2147903C1/en active
-
1999
- 1999-03-31 DE DE19914780A patent/DE19914780C2/en not_active Expired - Lifetime
- 1999-04-16 NO NO19991852A patent/NO312909B1/en not_active IP Right Cessation
- 1999-04-20 US US09/294,716 patent/US6264772B1/en not_active Expired - Lifetime
- 1999-04-27 CA CA002270027A patent/CA2270027C/en not_active Expired - Lifetime
- 1999-06-07 EP EP99110884A patent/EP0976424B1/en not_active Expired - Lifetime
- 1999-06-07 DE DE69907332T patent/DE69907332D1/en not_active Expired - Lifetime
- 1999-06-11 AU AU34998/99A patent/AU762661B2/en not_active Expired
- 1999-07-28 BR BR9903014-4A patent/BR9903014A/en not_active IP Right Cessation
-
2001
- 2001-01-05 US US09/754,109 patent/US20010011567A1/en not_active Abandoned
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US20100078098A1 (en) * | 2002-08-05 | 2010-04-01 | Daicel Chemical Industries, Ltd. | Gas generating composition for inflator containing melamine cyanurate |
WO2009006766A1 (en) | 2007-07-10 | 2009-01-15 | Shaanxi J&R Fire Fighting Co., Ltd | Fire-extinguishing aerosol for heavy-current electric appliance |
WO2009006767A1 (en) | 2007-07-10 | 2009-01-15 | Shaanxi J&R Fire Fighting Co., Ltd | Fire-extinguishing aerosol for common electric appliance |
WO2009006765A1 (en) | 2007-07-10 | 2009-01-15 | Shaanxi J&R Fire Fighting Co., Ltd | Fire-extinguishing aerosol for precision electric appliance |
US20120273711A1 (en) * | 2010-01-19 | 2012-11-01 | Shaanxi J & R Fire Fighting Co. Ltd. | Novel aging-resistant aerosol generating agent and a preparation method thereof |
US8721911B2 (en) * | 2010-01-19 | 2014-05-13 | Shaanxi J & R Fire Fighting Co., Ltd. | Aging-resistant aerosol generating agent and a preparation method thereof |
US20120034482A1 (en) * | 2010-08-06 | 2012-02-09 | Atoz Design Labs Co., Limited | Fire extinguishing material and fabrication method thereof |
CN102258836A (en) * | 2011-05-11 | 2011-11-30 | 浙江威龙高分子材料有限公司 | Flame-retarding fire extinguishing agent for coal mines |
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Also Published As
Publication number | Publication date |
---|---|
AU3499899A (en) | 2000-02-24 |
CA2270027A1 (en) | 2000-01-30 |
CA2270027C (en) | 2008-07-22 |
EP0976424B1 (en) | 2003-05-02 |
EP0976424A1 (en) | 2000-02-02 |
DE69907332D1 (en) | 2003-06-05 |
US6264772B1 (en) | 2001-07-24 |
NO991852L (en) | 2000-01-31 |
BR9903014A (en) | 2000-03-28 |
NO312909B1 (en) | 2002-07-15 |
AU762661B2 (en) | 2003-07-03 |
RU2147903C1 (en) | 2000-04-27 |
DE19914780C2 (en) | 2002-12-19 |
NO991852D0 (en) | 1999-04-16 |
DE19914780A1 (en) | 2000-02-03 |
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Legal Events
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |