EP0570413B1 - Agent extincteur et protecteur contre le feu - Google Patents

Agent extincteur et protecteur contre le feu Download PDF

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Publication number
EP0570413B1
EP0570413B1 EP92903639A EP92903639A EP0570413B1 EP 0570413 B1 EP0570413 B1 EP 0570413B1 EP 92903639 A EP92903639 A EP 92903639A EP 92903639 A EP92903639 A EP 92903639A EP 0570413 B1 EP0570413 B1 EP 0570413B1
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EP
European Patent Office
Prior art keywords
water
fire
fire extinguishing
extinguishing
thickened
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92903639A
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German (de)
English (en)
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EP0570413A1 (fr
Inventor
Jürgen Buil
Gernot LÖHNERT
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Individual
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Individual
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Filing date
Publication date
Priority claimed from DE19914103388 external-priority patent/DE4103388A1/de
Priority claimed from DE19914118888 external-priority patent/DE4118888A1/de
Priority claimed from DE19914134870 external-priority patent/DE4134870A1/de
Application filed by Individual filed Critical Individual
Publication of EP0570413A1 publication Critical patent/EP0570413A1/fr
Application granted granted Critical
Publication of EP0570413B1 publication Critical patent/EP0570413B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0064—Gels; Film-forming compositions
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0028—Liquid extinguishing substances
    • A62D1/005—Dispersions; Emulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof

Definitions

  • water As an extinguishing agent, water has the advantages of high heat absorption capacity and thus a favorable cooling effect, non-existent toxicity, compatibility with many flammable substances, good value for money and usually good availability. It is therefore still very important as a fire extinguishing agent.
  • a known disadvantage of water as an extinguishing agent is its thin liquid, through which large quantities flow unused during the extinguishing process and sometimes cause unnecessary water damage. This means that only a small part of the sprayed water can exert its beneficial extinguishing effect, which consists in cooling the fire material. There have therefore been many attempts to improve water as a fire extinguishing agent.
  • Incombustible mineral additives to the extinguishing water are also used, for example water-soluble inorganic salts or water-insoluble minerals such as bentonite or attapulgite.
  • water-soluble inorganic salts or water-insoluble minerals such as bentonite or attapulgite.
  • extinguishing water preparations containing for example bentonite, attapulgite and water-soluble salts as well as alginates are used, which after special preparation are often thrown off from aircraft.
  • extinguishing agents have practically no significance as generally applicable fire extinguishing agents.
  • the reasons for this are, for example, the generally high proportions by weight of the mineral additives required to achieve a sufficiently high thickening (e.g.
  • suspensions of amorphous synthetic silicas in water tend to agglomerate particles and sedimentation over time (usually over weeks or months), but this "thickening effect" is due to its slowness and its small size for the task at hand insignificant. This process, even if it can be accelerated somewhat by adding electrolytes, does not offer a solution to the task at hand.
  • Such suspensions, thickened by standing, become thin again by stirring even after a longer storage period, that is to say that this thixotropic liquefaction is also disadvantageous when spraying in the conventional fire extinguishing syringes, since it adversely affects the adhesion in this way thickened water severely affected.
  • a 4% slurry of pyrogenic silica in water for example, becomes thin again even after thickening due to storage during spraying.
  • an additive based on the total amount of the fire extinguishing agent , of polyethylene glycols and / or polyoxyethylene of molecular weights from> 700 to ⁇ 600,000 or of derivatives of polyethylene glycol or polyoxyethylene such as polyoxy
  • the required silica concentrations in water are only very low, they are only a fraction of the proportions otherwise required for thickening in aqueous slurry, namely 1-7% compared to> 10% otherwise.
  • Preferably 2-7% by weight of amorphous silica and 0.007 to 0.5% by weight of the additive are used.
  • the additives mentioned can be added to the low-viscosity slurry of silica in water, but can also be premixed dry with the water itself, but also with the silica.
  • a compressed extinguishing water that can be used at the moment is obtained, which is thickened significantly in a controlled manner, for example by the shear effect present in a fire extinguishing pump, without the spraying performance suffering as a result.
  • the flow properties of the thickened extinguishing water improve its spraying properties, for example its throwing distance or the lower frictional losses, compared to ordinary water.
  • the thickened water as described has a number of essential advantages, such as good sprayability or sprayability by means of different types of fire extinguishing syringes according to DIN (bucket sprayer / TS 2/5) also by means of a high pressure pump with a working pressure of 100 bar, applicability from hand-held fire extinguishers, liability Even thick layers of extinguishing agent from several centimeters thick to evaporation or drying, even on vertical and downward-facing surfaces of different materials and properties. After the fire-fighting measures have been completed, the extinguishing agent can be removed easily and without damaging the respective subsurface, for example by spraying with water or by suction using a conventional industrial vacuum cleaner.
  • the thickened extinguishing water Since most of the thickened extinguishing water is not lost through running, it can be taken up again after the extinguishing process, thus limiting contamination of the environment by fire products that may run off with the extinguishing water or water damage to buildings will.
  • the remaining silica gel After drying, the remaining silica gel has adsorbing properties, which can also be advantageous, for example, for absorbing decomposition products from the fire process or other contaminants. It is particularly advantageous to use this property of the fire extinguishing agent according to the invention by sucking in the dry premix of the amorphous silica with the thickener into a stream of extinguishing water, the desired thickening currently occurring. It is noteworthy that an addition of little more than 1%, for example pyrogenic silica, into the water is sufficient for this.
  • silica in water can also be advantageous for certain applications, for example to create a barrier with the extinguishing agent against the uncontrolled drainage of liquids from the fire area or to use the absorbing effect of the silica for any existing pollutants.
  • pastes which can no longer be applied form with the conventional extinguishers, but which can be used as fire protection compositions, since they maintain their homogeneity even with a high water content and low silica content.
  • a silica gel obtained from water glass by neutralization and washing or by ion exchange and set in paste form is homogeneous only shortly after production and soon begins to separate out a considerable amount of water.
  • the fire protection composition produced according to the invention avoids this phenomenon with a high water and low solids content.
  • These fire protection compounds are versatile for preventive fire protection of flammable structures, in fire-retardant barrier elements or cable trays, especially those that are sensitive to corrosion, fire decomposition products or water that flows out.
  • the "thickening additives" used according to the invention are only required in extremely low weight concentrations in all cases. With preferably used proportions of only 0.007-0.5% by weight based on the total amount, they almost do not fall more weight.
  • Various of the thickening additives described are usually used as emulsifiers, for example for fats, waxes or as special surfactants.
  • the "flocculation" of silica with polyglycol is considered useful, for example, for water clarification.
  • polyethers as thickening additives are weakly alkaline compounds, such as the bicarbonates. These are compatible with the densified slurries of amorphous synthetic silica in any soluble concentration. Potassium bicarbonate, for example, can be added up to its saturation concentration of approximately 34%. When extinguished, these bicarbonates can decompose and release carbon dioxide, which increases the extinguishing effect.
  • the thickened slurries of amorphous, synthetic silica according to the invention are also compatible with other, not strongly alkaline salts, for example the preparation can also be done with sea water without difficulty, or potassium sulfate, ammonium phosphate or boric acid can be dissolved in the thickened slurry.
  • thickening additive causes polyethyleneimine to have a durable thickening effect in the aqueous silica slurry in all alkaline areas, a re-liquefaction can be observed with polyethyleneimine in the strongly acidic area. Acidic conditions are avoided anyway in order to avoid corrosion. If required, however, a combination of both thickening additives is possible, which can be used to thicken in the acidic and alkaline range.
  • pyrogenic silica (Aerosil 200, reg. Trademark. Degussa, Germany) are slurried in 190-196 ml of water with stirring. The resulting suspensions are thin with a pH of around 5. If they are not stirred vigorously, their run-down times in the DIN cup (4 mm nozzle) are 9-11 seconds, and the run-down time can be as long as there are slight clumps 14 seconds. If you stir them with an electric stir bar (approx. 800 rpm), they become even thinner with a flow time of 9 seconds, comparable to the viscosity of the water.
  • polyoxyethylene lauryl ether with a molecular weight of approximately 380 or a 50% aqueous solution of polyethylene glycol with a molecular weight of 4220 or a 50% aqueous solution of polyoxyethylene sorbitan monostearate with a molecular weight of approximately 1200 or a concentrated solution of PEG- are added to these suspensions.
  • 120 jojoba acid and PEG-120 jojoba alcohol mainly eicosenyl or docosenylic acid / alcohol from jojoba oil, ethoxylated
  • a 20% polyethyleneimine solution Polymin SK, reg. WZ. BASF, Ludwigshafen, Germany
  • pyrogenic silica 4-10 g are mixed with 0.3 g of polyoxyethylene lauryl ether or polyethylene glycol of molecular weight 4220, or polyethylene glycol sorbitan monostearic acid ester (molecular weight approx. 1200) or PEG-120 jojoba acid and PEG-120 jojoba alcohol or polyethyleneimine, so that a dry premix is obtained.
  • an electric stir bar blade diameter 3.5 cm, approx. 800 rpm
  • the properties of the thickened silica slurries obtained show no differences from those obtained according to Example 1 in comparable concentrations.
  • 100 g of a dry premix of pyrogenic silicic acid (97 g) and polyoxyethylene lauryl ether (3 g) obtained according to this example is filled into a storage vessel and placed in a storage tube via a suction hose, which has a pipe connection to a running water stream, by means of a slight vacuum into this Water flow sucked in, whereupon mixing and thickening occur, so that the water emerging from a slightly narrowed glass nozzle just a few centimeters after the mixing point already had excellent adhesion to a glass surface.
  • the suction side of a water jet pump can also be used to suck in the dry premix, wherein the suction of the powdery premix can be continued for a long time without problems or blockages.
  • the thickening method can be controlled as desired by appropriately dimensioning the suction feeds, regulating the amount of water and the water pressure. A useful thickening according to this procedure is achieved, for example, with a silica concentration of only 1.3% in water.
  • the thickened silica slurries obtained according to Examples 1 and 2 were each mixed with 5% by weight of sodium carbonate and borax, so that pH values of 11 or were obtained from 9.1. While the thickening in all polyoxyethylene derivatives disappeared immediately after the addition, it was permanently retained in the silica slurries thickened with polyethyleneimine.
  • the thickened silica slurries obtained according to Examples 1 and 2 were each mixed with small amounts of hydrochloric acid until pH 1 was reached and with 2% citric acid or ascorbic acid until pH 2 and 3 were reached.
  • the thickening remains with all polyoxyethylene compounds in these acidic areas. Reliquefaction, however, is observed with those mixed with polyethyleneimine.
  • Example 6 production and application with a bucket syringe
  • Example 2 It can be thickened by the additives mentioned in Example 1 and converted into a thickened aqueous slurry of silica suitable as an adhering fire extinguishing agent.
  • the other part of the batch was mixed with 250 g of polyoxyethylene lauryl ether immediately after production and stirred with a paddle stirrer, which led to the uniform thickening of the entire silica suspension within about 30 seconds.
  • the thickened, sprayed extinguishing water could be picked up again after use by scooping or suctioning, so that any fire by-products contained therein did not get into the ground or only to a considerably reduced extent.
  • a test fire with solid fuels of fire class A (wooden crib, 40x40 cm, 7 layers, pre-burning time 4 min) was extinguished with a spray jet using thickened extinguishing water, prepared according to Example 7, adjusted to 2.5 and 3% SiO2 content.
  • thickened extinguishing water prepared according to Example 7, adjusted to 2.5 and 3% SiO2 content.
  • only 1/4 of the amount of extinguishing agent was used for extinguishing and the number of reignitions also decreased to 1/4.
  • the adhesive layer of the thickened extinguishing water delays or prevents the spread of fire and ignition of the parts of the combustible material that have not yet been affected by the fire.
  • the agent is suitable for extinguishing flammable materials such as wood, plastic, rubber, wood-based materials, textiles and other organic solid substances.
  • a 13-A fire (according to BFS 5423) was extinguished with a 3% thickened silica slurry prepared according to Example 7 extinguishing water preparation.
  • the consumption of the extinguishing agent until it was completely extinguished was only 1.7 kg. This means that only 50 grams of silica have been used to completely extinguish the fire.
  • the amount of firewood used here can naturally contain several times this amount of silica in its ashes.
  • a low-viscosity slurry of 4% of pyrogenic silica in water without the thickening additives described was used to extinguish a test fire of fire class A (as in example 8).
  • the unthickened slurry used only marginally less to achieve the same quenching result.
  • the number of reignitions obtained was comparable to that obtained with water itself. This shows that the good quenching effect found is dependent on the presence of a thickened aqueous slurry of the amorphous, synthetic silica.
  • 500 ml of an approximately 3% silica sol are prepared from a sodium water glass solution by treatment with a strongly acidic cation exchanger.
  • the pH of the sol is approximately 5.
  • the sol is exposed to shear for 5 minutes in a blender. There is no visible change.
  • the silica sol immediately thickens without becoming gelatinous and has a viscosity of 20 Seconds in the outlet cup, remains sprayable and adheres to surfaces.
  • the viscosity is still 14-15 seconds. So there seems to be a slight thixotropy, but this is not disadvantageous for the spraying.
  • silica sol 500 ml of an approx. 7% silica sol are produced from a sodium water glass solution by treatment with a strongly acidic cation exchanger. The pH of the sol is approx. 5. The silica sol is left to gel and the resulting gel is stored for two weeks. A 3% slurry in water was then prepared in a blender, which was sprayable and showed good adhesion. Its viscosity is 18 seconds in a DIN cup with a 4 mm nozzle.
  • a slurry adjusted by dilution from an approx. 3% slurry of amorphous silica in water to approx. 2.5% silica content had an outlet viscosity of approx. 14-15 seconds.
  • This slurry was used to extinguish a standardized Class A fire.
  • the amount of extinguishing agent required was 1/3 of that of the water used as the reference extinguishing agent, and the number of flashbacks compared to water was reduced to half.
  • a slurry of 8 g Aerosil 200 in 150 ml water was prepared. 80 g of 35 g of propylene glycol (A) and 69 g of 46 g of propylene glycol (B) are added to this. A and B are each thickened by adding 4 drops of polyoxyethylene lauryl ether. Both are kept in the refrigerator at -12 ° C for 48 hours, where B is viscous and A is syrupy appeared viscous. After thawing, the thickening obtained after the addition of the thickener was retained as from the freezing.
  • Aerosil 200 6 g are slurried in a solution of 10 g of potassium sulfate in 195 g of water and a few drops of polyoxyethylene lauryl ether are added to the resulting thin suspension and the mixture is stirred. The resulting thickening is expressed in an outlet viscosity of 20 seconds in a DIN cup (4 mm).
  • 83 g of water are mixed with 7 g of pyrogenic silica and 0.1 g of polyethyleneimine (or the same amount of fatty alcohol polyglycol ether of the MG> 300, fatty acid polyglycol ester of the MG> 300, Polyoxyethylene sorbitan monofatty acid ester, or polyethylene glycol of MW> 700) and mixed by stirring.
  • the resulting paste is filled into a plastic bag.
  • the thickness of the pillow thus produced is approximately 8 mm, the dimensions approximately 10 x 10 cm.
  • Pieces of cable of various diameters are placed on the pillow. A horizontal gap of 3 cm in width is covered with this pillow. The gap is then flamed from below with a gas burner. Temperatures of approx. 700 ° C arise on the underside of the cushion. The cables are intact after flame exposure for approx. 20 min.
  • a pillow as described in Example 17 is made with an insert made of a plastic grid. At the ends of this pillow is provided with Velcro fasteners. The resulting pillow is placed around a polypropylene tube with a diameter of 40 mm according to DIN 19560 and closed with the Velcro like a sleeve. The tubular part protected in this way is flamed from below with a fire generated by gasoline in such a way that the flames sweep past the tube or the sleeve on both sides. After 20 minutes, the pipe shows no damage or softening.
  • a pillow, as described in Example 17, is filled with a paste with the addition of 10 g of sugar dissolved in water.
  • the pillow is hung upright and flamed from the front with a gas burner.
  • a cable behind it is intact after 20 minutes.
  • a precipitated silica 10.5 g are slurried in 150 ml of water. 0.2 g of polyethyleneimine are added to this thin slurry and stirred well. The slurry thickens and has an outlet viscosity of 18 seconds.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Management (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Fireproofing Substances (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (9)

  1. Procédé de production d'un agent d'extinction et d'ignifugation à base d'eau épaissie, caractérisé en ce qu'on prépare une suspension épaissie d'acide silicique synthétique amorphe dans de l'eau ayant une teneur pondérale en acide silicique d'au moins 1 à 9 % au maximum avec addition de 0,003 à 1,5 % en poids d'un additif, par rapport au poids total de l'agent d'extinction, formé de polyéthylène glycols et/ou de polyoxyéthylène de masses molaires supérieures à 700 et inférieures à 600.000 ou de dérivés de polyéthylène glycol ou de polyoxyéthylène tels que des éthers d'alcools gras de polyoxyéthylène, d'esters d'acides gras de polyoxyéthylène ou de leurs mélanges, ainsi que d'esters d'acides gras et d'alcools sacchariques de polyoxyéthylène de masses molaires de 300 ou davantage, ou de polyéthylèneimines, comme agent épaississant, l'épaississement et l'adhésivité pouvant être renforcés par l'opération d'injection avec des appareils extincteurs usuels ou par un processus d'agitation ou de mélange intensif.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise 2 à 7 % en poids d'acide silicique amorphe et 0,007 à 0,5 % en poids de l'additif.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on ajoute en outre des substances formatrices d'ossatures carbonées.
  4. Procédé selon au moins une des revendications 1 à 3, caractérisé en ce que l'on ajoute en outre des substances améliorant l'action d'extinction telles que, par exemple, des carbonates acides, des borates ou des phosphates d'ammonium.
  5. Agent d'extinction et d'ignifugation, produit selon au moins l'une des revendications 1 à 4.
  6. Utilisation de l'agent d'extinction et d'ignifugation constitué d'eau épaissie selon la revendication 5, caractérisée en ce que l'agent est utilisé comme agent d'extinction dans des extincteurs usuels.
  7. Utilisation de l'agent d'extinction et d'ignifugation constitué d'eau épaissie selon la revendication 5, caractérisée en ce que l'agent est appliqué en tant que source d'agent extincteur sur l'objet combustible ou risquant de brûler auquel il se fixe par son action adhésive et, par suite, le risque d'extension du feu est évité et l'effet d'extinction de l'eau est prolongé en l'empêchant de couler.
  8. Utilisation de l'agent d'extinction et d'ignifugation constitué d'eau épaissie selon la revendication 5, caractérisée en ce que l'agent est utilisé dans des installations d'extinction fixes, des buses de pulvérisation et des raccords auxiliaires de secours.
  9. Utilisation de l'agent d'extinction et d'ignifugation constitué d'eau épaissie selon la revendication 5, caractérisée en ce que l'agent est disposé dans des enveloppes appropriées, par exemple sous la forme de coussins flexibles, sur les emplacements à protéger.
EP92903639A 1991-02-05 1992-02-04 Agent extincteur et protecteur contre le feu Expired - Lifetime EP0570413B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE4103388 1991-02-05
DE19914103388 DE4103388A1 (de) 1991-02-05 1991-02-05 Feuerloeschmittel
DE4118888 1991-06-10
DE19914118888 DE4118888A1 (de) 1991-02-05 1991-06-10 Feuerloeschmittel
DE19914134870 DE4134870A1 (de) 1991-10-23 1991-10-23 Brandschutzmasse
DE4134870 1991-10-23
PCT/DE1992/000070 WO1992013602A1 (fr) 1991-02-05 1992-02-04 Agent extincteur et protecteur contre le feu

Publications (2)

Publication Number Publication Date
EP0570413A1 EP0570413A1 (fr) 1993-11-24
EP0570413B1 true EP0570413B1 (fr) 1996-01-31

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EP92903639A Expired - Lifetime EP0570413B1 (fr) 1991-02-05 1992-02-04 Agent extincteur et protecteur contre le feu

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EP (1) EP0570413B1 (fr)
AT (1) ATE133573T1 (fr)
AU (1) AU1184392A (fr)
CA (1) CA2101947A1 (fr)
DE (2) DE4290321D2 (fr)
WO (1) WO1992013602A1 (fr)

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WO2011013009A2 (fr) 2009-07-29 2011-02-03 Foamix Ltd. Compositions hydro-alcooliques moussantes non tensioactives, mousses légères, et leurs utilisations
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US9849142B2 (en) 2009-10-02 2017-12-26 Foamix Pharmaceuticals Ltd. Methods for accelerated return of skin integrity and for the treatment of impetigo
DE102013112063A1 (de) 2013-11-01 2015-05-07 Viktor Bauf Brandschutz- oder brandhemmende Zusammensetzung und deren Verwendung
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Publication number Publication date
CA2101947A1 (fr) 1992-08-06
WO1992013602A1 (fr) 1992-08-20
DE4290321D2 (de) 1994-04-28
EP0570413A1 (fr) 1993-11-24
ATE133573T1 (de) 1996-02-15
DE59205254D1 (de) 1996-03-14
AU1184392A (en) 1992-09-07

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